Corrosion Chemistry PDF

Corrosion Chemistry
George R . B r u b a k e r ,
EDITOR
Illinois Institute of Technology

P. Beverley P . Phipps,
IBM
EDITOR
Corporation
Based on a 1976 lecture series

sponsored by the Chicago Sections
of the American Chemical Society
and the Electrochemical Society.
89
ACS SYMPOSIUM SERIES
AMERICAN
CHEMICAL
SOCIETY
WASHINGTON, D. C. 1979
In Corrosion Chemistry; Brubaker, G., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1979.
Library of Congress CIP Data

Corrosion chemistry.
(ACS symposium series; 89
Includes bibliographical references and index.
1. Corrosion and anti-corrosivesAddresses, essays,
lectures.
I. Brubaker, George R., 1939. II. Phipps, Peter
Beverley, 1936. III. American Chemical Society,
Chicago Section. IV. Electrochemical Society. Chicago
Section. V . Series.
TA418.74.C595
ISBN 0-8412-0471-3
620.1'6'23
ASCMC 8
78-25554
89 1-424 1979
Copyright 1979
American Chemical Society
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PRINTED IN THE UNITED STATES OF AMERICA

ACS Symposium Series

R o b e r t F. G o u l d , Editor
Advisory Board
Kenneth B. Bischoff
James P. Lodge
Donald G . Crosby
John L. Margrave
Robert E. Feeney
Leon Petrakis
Jeremiah P. Freeman
F. Sherwood Rowland
E. Desmond Goddard
Alan C. Sartorelli
Jack Halpern
Raymond B. Seymour
Robert A. Hofstader
Aaron Wold
James D. Idol, Jr.
Gunter Zweig

FOREWORD
The A C S
S Y M P O S I U M
SERIES
w a s f o u n d e d i n 1 9 7 4 to p r o v i d e
a m e d i u m for p u b l i s h i n g symposia q u i c k l y i n book form.

f o r m a t of the
I N
C H E M I S T R Y
SERIES
p a r a l l e l s that of the c o n t i n u i n g
SERIES
The
A D V A N C E S
except t h a t i n o r d e r to save t i m e t h e
papers are n o t typeset b u t are r e p r o d u c e d as t h e y are s u b m i t t e d b y t h e authors i n c a m e r a - r e a d y f o r m .
A s a further
means of s a v i n g t i m e , t h e papers are n o t e d i t e d o r r e v i e w e d

except b y t h e s y m p o s i u m c h a i r m a n , w h o b e c o m e s e d i t o r of
the book.
Papers p u b l i s h e d i n the A C S
S Y M P O S I U M
SERIES
a r e o r i g i n a l c o n t r i b u t i o n s not p u b l i s h e d elsewhere i n w h o l e o r
m a j o r p a r t a n d i n c l u d e reports of r e s e a r c h as w e l l as r e v i e w s
since s y m p o s i a m a y e m b r a c e b o t h types of p r e s e n t a t i o n .

PREFACE
his v o l u m e records the p r o c e e d i n g s of a t w e l v e l e c t u r e short c o u r s e
j o i n t l y s p o n s o r e d b y t h e C h i c a g o Sections of t h e A m e r i c a n C h e m i c a l
S o c i e t y a n d t h e E l e c t r o c h e m i c a l Society.
T h e lectures c o v e r e d s e v e r a l
aspects of c u r r e n t w o r k i n c o r r o s i o n ; t h e y w e r e a d d r e s s e d to p h y s i c a l
chemists a n d c h e m i c a l engineers as w e l l as t o c o r r o s i o n specialists a n d
surface scientists. R e a d e r s f r o m e a c h of these d i s c i p l i n e s w i l l find s e v e r a l
p a r t s of t h e w o r k d e s c r i b e d h e r e c h a l l e n g i n g a n d i n f o r m a t i v e .
T h e s t u d y of c o r r o s i o n has u n d e r g o n e s u b s t a n t i a l e x p a n s i o n i n t h e
p a s t d e c a d e i n response t o n e w t e c h n i q u e s of s t u d y a n d to d e m a n d s f o r
n e w m a t e r i a l s to w i t h s t a n
expanded applications o
ods f o r more-or-less r o u t i n e surface analysis. E x a m p l e s i n w h i c h c o n s i d e r a t i o n of c o r r o s i o n has h a d a m a j o r i m p a c t o n the d e v e l o p m e n t of n e w
m a t e r i a l s i n c l u d e h i g h t e m p e r a t u r e t u r b i n e s , a i r f r a m e structures, e l e c t r o n i c a p p l i c a t i o n s of t h i n m e t a l films, a n d e n e r g y d e v e l o p m e n t p r o g r a m s
s u c h as c o a l gasification. T h i s v o l u m e c o n t a i n s chapters r e l a t e d to a p p l i cations a n d r e v i e w s of f u n d a m e n t a l research. T h e i m p a c t of n e w e l e c t r o c h e m i c a l a n d surface c h a r a c t e r i z a t i o n m e t h o d o l o g y is seen t h r o u g h o u t
t h e text.
Sections o n e l e c t r o c h e m i s t r y a n d h i g h t e m p e r a t u r e c o r r o s i o n
w i l l i n t r o d u c e those u n f a m i l i a r w i t h these areas to n e w concepts.
This
v o l u m e c l e a r l y illustrates the e m p i r i c a l f o u n d a t i o n s of c o r r o s i o n c h e m istry, y e t a p p l i c a t i o n s of s o l i d state t h e o r y t o i o n i c a n d e l e c t r o n i c c o n d u c t i o n i n solids, f o r e x a m p l e e m e r g e i n s e v e r a l chapters.

T h e editors t h a n k the a u t h o r of e a c h c h a p t e r for his or h e r w o r k ,
w h i c h i n m a n y cases i n v o l v e d s u b s t a n t i a l r e w r i t i n g of t h e o r a l p r e s e n t a t i o n ; R u d o l p h H . H a u s l e r f o r o r g a n i z i n g the l e c t u r e series; M s . D o r o t h y
H u b e r f o r t a p e d t r a n s c r i p t s of t h e p r o c e e d i n g s ; the staff of t h e C h i c a g o
S e c t i o n f o r m a n a g e m e n t of the l e c t u r e series; a n d t h e i n s t i t u t i o n s f o r
w h i c h w e w o r k f o r a l l o w i n g us the o p p o r t u n i t y t o b r i n g this v o l u m e
together.
I l l i n o i s I n s t i t u t e of T e c h n o l o g y
G E O R G E
BRUBAKER
Chicago, Illinois
IBM
Corporation
B E V E R L E Y PHIPPS
S a n Jose, C a l i f o r n i a
S e p t e m b e r , 1978
vii

Corrosion: The Most General Problem of Materials

Science
DONALD TUOMI
Solid State Physics, Roy C. Ingersoll Research Center, Borg-Warner Corp.,
Des Plaines, IL 60016
The following chapters systematically address
varied aspects of the field known as corrosion.
In
this introductory overview
effor w i l l b mad
touch only lightl
- the most general problem of materials science.
For the f i r s t step to developing an overview, a
meaning to the word corrosion needs expression. To my
wife, corrosion means that there is a dirty brown
splotch on the side of the car which means it is worn
out and time to trade in is here. They don't make them
as well as before ! This brings our attention to the
classic meaning of corrosion as being a loss in value
for some solid object which has been suffering from
chemical attack at the surface. I suspect that for
many this feeling of decreased value through corrosion
leads to a negative feeling towards the topic. Corrosion, in general, is used to describe degradation in
value of useful objects.
An alternative perspective is present in corrosion
engineer anecdotes. "Nope, we don't have any corrosion
problems in this plant. The pumps wear out every six
weeks and we replace them." Or alternatively, "We just
dump the scrap here and as soon as we can fill a railroad car we haul it to a hole a hundred miles away and
bury it. Some day when the corrosion finishes the junk
off, we'll build condominiums on the land." Or yet
another one - "Hey, would you believe that with six
months' data they want me to warrant that tank for 50
years of radioactive waste storage?" Yes, these do
represent some famous last words. Enough for the anecdotal description; we are not gathered here to be
entertained.
Corrosion is a serious, costly materials science
problem. In the years ahead as our resources are
increasingly utilized to the limits of practicality,
1
0-8412-0471-3/79/47-089-001$08.50/0
1979 American Chemical Society

CORROSION
CHEMISTRY
and c o n s e r v a t i o n and r e c y c l i n g a r e watchwords, n o t

c a t c h w o r d s ; t h e c o r r o s i o n e n g i n e e r w i l l be a t t h e
forefront.
May I emphasize a g a i n t h e t i t l e , " C o r r o s i o n :
The
Most G e n e r a l P r o b l e m o f M a t e r i a l s S c i e n c e . " So many I
e n c o u n t e r speak i n a d i s p a r a g i n g v o i c e about c o r r o s i o n
problems - t h a t i t * s j u s t a b l a c k a r t - w i t h o u t s u p p o r t ive science.
J u s t go i n t h e r e and do y o u r t h i n g d o n ' t b o t h e r me w i t h t h e f a c t s . As a m a t t e r o f f a c t ,
however, t h e r e i s so much s c i e n c e i n t h i s show t h a t a
c o n s t i p a t i o n o f words r e a d i l y s e t s i n b e f o r e t h e c o n s t i p a t i o n o f i d e a s i s even approached.
For t h e n e x t 90 m i n u t e s o r so l e t us e x p l o r e t h i s
f i e l d - CORROSION. We s h a l l t r a v e l i n two d i s t i n c t
ways. One i s t o b r i n g y o u r a t t e n t i o n t o a r r a y s o f k e y
words and c o n c e p t s . The o t h e r i s t o f o r m u l a t e a p a t t e r n
of s o l i d s t a t e surfac
be u s e f u l a s a framewor
and f o r e x p l o r i n g new o p t i o n s .
The l a t t e r w i l l be
w i t h i n two a r e a s : (1) exchange c u r r e n t d e s c r i p t i o n s o f
c o r r o s i o n p o t e n t i a l s and (2) t h e n a t u r e o f c o r r o d i n g
surfaces.
The e m p i r i c i s m t h a t a p p e a r s t o f o l l o w t h e c o r r o s i o n e n g i n e e r a r i s e s from t h e m u l t i - f a c t o r , m u l t i component s i t u a t i o n s w h i c h a r e p r e s e n t w i t h i n a l l
common a r t i c l e s o f commerce, be t h e y made from i r o n ,
aluminum, o r more e x o t i c m a t e r i a l c o m b i n a t i o n s . The
variables are continually interacting i n increasingly
complex ways so we can become e n g r o s s e d f o r even a l i f e t i m e w i t h j u s t one p r o b l e m i n p e r f o r m a n c e such as a i r f o i l stress corrosion
c r a c k i n g , b o i l e r feed water
s t a b i l i z a t i o n s , o r c o r r o s i o n i n h i b i t i n g p a i n t s , and
many more. B u t does t h i s mean t h e work l a c k s f o r
glamour and e x c i t e m e n t ?
W e l l , t h e m a t e r i a l s engineer i s f r e q u e n t l y caught
with orders t o s e l e c t materials combinations i n a pract i c a l s i t u a t i o n g i v i n g desired property balances with
adequate p e r f o r m a n c e d e s i g n e d t o f i r s t o r t o l i f e c o s t s .
A l t e r n a t i v e l y , he s e l e c t s model Mark I I m a t e r i a l s t o
c o v e r model Mark I m i s t a k e s . More i m p o r t a n t t o d a y ,
m a t e r i a l s e l e c t i o n s must a v o i d w a r r a n t y p a y o u t s c a p a b l e
o f c o r p o r a t e b a n k r u p t c y as w e l l a s extended p e r s o n a l
liability.
How i n d e e d a r e R & D d a t a p r e d i c t i n g f i e l d
r e l i a b i l i t y ? What i s a v a l i d t e s t ?
The c o r r o s i o n e n g i n e e r i s f r e q u e n t l y t h e pragmat i s t - so what i s t h e p r o b l e m - g e t r i d o f t h e o f f e n d ing material.
A n o t h e r approach i s "Hey, what c a n we
add t o , i n t r o d u c e t o , o r o t h e r w i s e c o a t t h e s y s t e m
w i t h so t h e p r o b l e m w i l l d i s a p p e a r l o n g enough t o
keep t h e c u s t o m e r s a d e q u a t e l y happy? Or a t l e a s t n o t

1.
Corrosion:
Problem
of
Materials
Science
s e r i o u s l y d i s a p p o i n t e d i n t h e v a l u e r e c e i v e d ? We c a n ' t
s e l l many g o l d - p l a t e d C a d i l l a c s . " Or t h e customer asks
how can I c h e a p l y save money i n t h e l o n g r u n w i t h o u t
paying the f a c t o r y ?
Ziebart i t !
W e l l , enough c o m m e r c i a l s - who i s t h i s c o r r o s i o n
e n g i n e e r and what i s he l i k e ? How many y e a r s has he
spent i n t h e i v o r y t o w e r s ?
Or has he e v e r v i s i t e d them?
W e l l , i f I had my d r u t h e r s , I would see t o i t t h a t
t h e c o r r o s i o n e n g i n e e r had a b i t o f f l a v o r i n g from
m a t e r i a l s s c i e n c e as shown i n F i g u r e 1. I n t h e s e days
of s p e c i a l i z a t i o n , i t would be n i c e t o t r a i n some generalists.
As an e x p e r t r e s p o n s i b l e f o r t h e f u t u r e
b e h a v i o r s o f most o f o u r s o l i d m a t e r i a l s , s u r e l y a
mastery o f t h e f u l l range c o v e r e d by c h e m i s t r y , p h y s i c s
m e t a l l u r g y , and j u s t a few o t h e r i n c i d e n t a l f i e l d s
would be c o n s i s t e n t w i t h a s s i g n e d r e s p o n s i b i l i t i e s . I f
he f e e l s a b i t s h o r t
t h e c o n s u l t a n t s and
ive t e c h n i c a l s o c i e t y .
What, you t h i n k t h e s u r v e y i s f a c e t i o u s and o u t o f
p l a c e ? L e t ' s t a k e a l o o k a t a c o r r o s i o n smorgasbord o f
t e r m i n o l o g y i n F i g u r e 2. The e x p e r i e n c e s o f a c o r r o
s i o n e n g i n e e r a r e r e p r e s e n t e d by t h e t e r m a r r a y . Sampl
ing
them a t random, i t seems t o be a j u m b l e .
However,
i t i s an o v e r v i e w .
Who, t h e n , i s t h e c o r r o s i o n e n g i n e e r ? F o r many
h e r e , he has an e x c i t i n g , r e s p o n s i b l e way o f d o i n g
complex m a t e r i a l s s c i e n c e i n s e r v i c e t o our s o c i e t y .
T h i s i n d i v i d u a l may n e v e r have d e l i b e r a t e l y p l a n n e d t h e
career which developed.
R a t h e r as a c i v i l e n g i n e e r , a
m e c h a n i c a l e n g i n e e r , a c h e m i s t , a p h y s i c i s t , an a n a l y s t ,
one day s u d d e n l y he has a r e s p o n s i b i l i t y t h r u s t on him
r e l a t i n g to materials r e l i a b i l i t y , to materials perfor
mance o r j u s t t o s o l v e t h a t p r o b l e m b e f o r e we a r e b r o k e .
Thus, many r o u t e s l e a d t o a c o r r o s i o n e n g i n e e r ' s
r e s p o n s i b i l i t y as i s r e f l e c t e d i n F i g u r e 3 .
He c o n
t r i b u t e s t o A P r i o r i P r o b l e m S o l v i n g b u t economics o f
f i r s t c o s t s f r e q u e n t l y l e a d t o P o s t - F a c t u m Problem
S o l v i n g . For, too o f t e n , c o r r o s i o n i s t i e d d i r e c t l y
t o systems' weakest l i n k v a r i a b l e s . Much o f t h e needed
knowledge i s absorbed a l m o s t by an osmosis p r o c e s s
because t h e r e j u s t a r e n ' t s i m p l e v a l i d d e s c r i p t i o n s o f
g e n e r a l use. A l l q u i c k l y become s p e c i f i c .
L a d i e s and gentlemen - i f you were t o examine t h e
agenda f o r t h e n e x t few weeks, q u i c k l y a r e c o g n i t i o n
w o u l d d e v e l o p t h a t t h e key-words have t o u c h e d on t h e
program e x p o s u r e s each w i l l e x p e r i e n c e - can you see
t h e beauty o f t h e t o u g h e s t m a t e r i a l s s c i e n c e problems
emerging t h r o u g h t h e program?


Chemistry
Chemistry
Physics
Consultants
Metallurgy
Ceramics
ENGINEER
CORROSION
Polymer
Figure 1.
Corrosion engineer
Thermo
Analysis
Design
Colleagues
Experimental
Instrumentation
Instrumental
Irreversible
Quantum Mechanics
Mechanics
Chemistry
Statistical
Electronics
S t a t i s t i c a l A n a l y s i s o f Experiments
Semiconductor P h y s i c s
D i f f u s i o n Transport
Hydrodynamics = L-G-S
Civil
Mechanical )
' Engineering
Electrical '
Chemistry
Thermodynamics
Analytical
SURFACE AND SOLID STATE MATERIALS SCIENCE
S o l i d State
Electrochemistry
Physical
INORGANIC AND ORGANIC CHEMISTRY

Water
Soil
i a l
Hot
Corrosion
Attack
- Cracking
Cruds
Flaking - Foliation
Layer
Crystalline
Granular
Corrosion
Inter
Trans
Stress Corrosion
Stress
Fatigue
Cracking
Inter
Trans
Oxidation
Dissolution
Salt
Atmospheric
Spray
Molten
L i q u i d Metal
Fuels
Salt
Action
Precipitation
Local C e l l
Chemical A c t i o n
Condensates
Action
Corrosion term smorgasbord
CORROSION
SMORGASBORD
Electrochemical
Figure 2.
Gases
Steam
Brines
F r e s h Water
Aerated
inorganic
Organic
Pipelines
Attack
Attack
Pitting
Crevicing
Intergranular
Intercrystalline
Grooving
General
Local
Inhibition
Corrosion Potentials
Equilibrium Potentials
Mixed P o t e n t i a l s
Confused P o t e n t i a l s
A c t i v e Surface
Passive Surface
Activation
Passivation
CORROSION
C H E M I S T R Y
THE CORROSION ENGINEER'S RESPONSIBILITY
Aesthetics
Environments
Economics
Performance
THE PROBLEM
A P r i o r i Materials Selection
C o r r o s i o n and Weakest L i n k
Figure 3.
Variables
Corrosion engineers responsibility

1.
TUOMi
Corrosion:
Problem
of
Materials
Science
L e t us l o o k a t a n o t h e r p a i r o f smorgasbord f i g u r e s
on c o r r o s i o n . The f i r s t , F i g u r e 4, f o c u s s e s l a r g e l y on ,
s u r f a c e phenomena from a p h y s i c a l c h e m i s t - e l e c t r o c h e m i s t
o r s u r f a c e c h e m i s t c o n t e x t . Do t h e words have a f a m i l i a r meaning? S h o u l d I d e f i n e a few o r perhaps we
should look at another, Figure 5 , which o u t l i n e s
a n o t h e r s e t o f , p r o b a b l y l e s s f a m i l i a r t o most, key
words. These are r e l a t e d t o t h e d e s c r i p t i o n o f s o l i d
s t a t e s t r u c t u r e s w h i c h a r e e n c o u n t e r e d on t h e s o l i d
side of the e l e c t r i c a l double l a y e r .
I t i s the d i s t u r b i n g phenomena p r o c e e d i n g w i t h i n t h e s o l i d s u r f a c e
s i d e t h a t g i v e s r i s e t o the d i v e r s e experiences of the
c o r r o s i o n engineer.
F o r an o v e r v i e w we c l e a r l y c o u l d spend much t i m e
on each word, l e a r n i n g what meaning was e x p e r i e n c e d by
each o f us.
Each would be s u r p r i s e d what a range
c o u l d be r e v e a l e d b
much o f t h e managemen
i n c l i n e d t o say, please p r a c t i c e your a r t w i t h o u t
f u l l y r e c o g n i z i n g o r e x p e r i e n c i n g t h e complex b e a u t y
present.
F o r i t i s o n l y a r t t o t h e b e h o l d e r - l e t us
continue s k e t c h i n g the canvas.
D i d you e v e r s t o p t o c o n t r a s t t h e c o n c e p t u a l i z a t i o n o f c h e m i s t s common models, o r f o r t h a t m a t t e r ,
most d e s c r i p t i o n s o f s o l i d m a t e r i a l b e h a v i o r s ?
In
F i g u r e 6 we are e x a m i n i n g the p h e n o m e n o l o g i c a l s i t u a t i o n o v e r w h i c h we spend so much t i m e p u z z l i n g .
The
m e n t a l images u s u a l l y do n o t a s s i g n d e t a i l e d s t r u c t u r e
t o t h e s o l i d phase. We can c l e a r l y see i t b e f o r e us
- i t i s so o b v i o u s .
The model we a r e u s u a l l y s p e a k i n g about i s shown
i n t h e lower l e f t c o r n e r - a s t r u c t u r e l e s s s o l i d
b e h a v i n g i n an e n v i r o n m e n t o f l i q u i d , o r gas, more
r a r e l y an i m p e r f e c t , impure vacuum. The l a t t e r e n v i ronment has t h e s p a t i a l e x t e n t .
More t r u l y as i n t h e l o w e r r i g h t c o r n e r t h e s o l i d
i s d e f i n e d by x-y-z c o o r d i n a t e s w h i c h d e f i n e what i s
a c t u a l l y happening where as a f u n c t i o n o f time i n an
experiment.
S t i l l more p r e c i s e l y , t h e s o l i d i n t h e e x p e r i m e n t
i s b e i n g space averaged t o produce the d a t a i n t h e
f i g u r e s above.
The s o l i d i s b e s t d e s c r i b e d g e n e r a l l y f o r t h e
c o r r o s i o n e n g i n e e r ' s p u r p o s e s as a
" p o l y p h a s e inhomogeneous s o l i d c o n t a i n i n g
h e t e r o g e n e i t y homogeneously d i s p e r s e d . "
The d e s c r i p t i o n i s r a t h e r p r e c i s e a c c o r d i n g t o Webster s
U n a b r i d g e d D i c t i o n a r y . T h i s r e f e r e n c e can be c i t e d i f
the statement r e q u i r e s s u b s t a n t i a t i o n .
Goodness, w i t h t h i s c o m p l e x i t y where do we go from
1


Ionic
Polarization
Fields
Fields
Kinetic
Double Layer
Planes
Potential
Ideal
Phase)
CORROSION
Content
Energy
Potentials
Loss
Open-Circuit Potentials
Short-Circuit
Potentials
Cell Potentials
Over P o t e n t i a l s
Anodic-Cathodic P o t e n t i a l s
Mixed P o t e n t i a l s
I R
Polarization Potentials
Activation Polarization
Concentration P o l a r i z a t i o n
Electrode
Entropy
Heat
Free
Oxidation-Reduction
Thermodynamic
Corrosion smorgasbord (continued)
Exchange C u r r e n t s
Potential
Electrochemical
Figure 4.
Polarizable
Non-Faradaic
Faradaic Processes
Constant
Constant C u r r e n t
Potential Transients
Compact Double Layer
Diffuse
The Helmholtz
E l e c t r i c Dipole F i e l d s
Atomic
(Liquid
Model Components
oo

Defects
Phase
Solutions
Bands
Figure 5.
Impurity
Potential
Bands
Bands
Dislocations
Fermi L e v e l s
Work F u n c t i o n s
Surface P o t e n t i a l s
Conduction
Corrosion smorgasbord (continued)
States
Defects
E l e c t r o n s and Holes
Surface
Surface
Charge T r a n s f e r
Catalysis
-Metal
Insulator-Semiconductor
Imperfections
Charge T r a n s p o r t
F l a t Band
Band S t r u c t u r e
CORROSION
Space Charge P o t e n t i a l
Valence
States
States
States
Trapping
Impurity
Dopant
Ionic-Covalent
Electronegativity
Solid Solutions
Metastable
Inhomogeneous-HeterogeneousHeterogeneity
Solid
Zeolite to Perfect C r y s t a l -
Associated
Imperfections
- Interstitials
Mass T r a n s p o r t
Vacancies
10
CORROSION
Figure 6.
CHEMISTRY
Phenomenological view of a one-dimensional solid contrasts with the

three-dimensional reality of most solid systems.

1.
Corrosion:
Problem
of
Materials
11
Science
h e r e ? W e l l , l e t s j u s t acknowledge t h a t t h i s has
a l w a y s been t h e s t a g e on w h i c h most o f us a r e a c t i n g
out our p r o f e s s i o n a l l i v e s .
Thus, i n F i g u r e 7, S o l i d s a r e d e s c r i b e d as b e i n g
i d e a l l y p e r f e c t v e r s u s i d e a l l y i m p e r f e c t w i t h most
being i n the l a t t e r category.
A sharp consequence was
t a u g h t t o me many y e a r s ago by L e r o y Dunham o f t h e
E d i s o n P r i m a r y B a t t e r y . When I s m a r t l y d e s c r i b e d a
s t a t i s t i c a l quantum-mechanics model o f c h a r g e t r a n s f e r
c a t a l y s i s o f oxygen r e d u c t i o n on an e l e c t r o d e s u r f a c e ,
he s m i l e d as i f he was e n j o y i n g h i m s e l f . He had been
f o r c e d t o l e a v e s c h o o l a t t h e e i g h t h grade l e v e l . ,
L a t e r i n t h e day as he and I s t r o l l e d t h r o u g h the
p r o d u c t i o n p l a n t making h i s e l e c t r o d e s , he q u i e t l y
s a i d , "Don, I e n j o y e d y o u r comments so v e r y much.
Back i n t h e '30*s when I was d o i n g the development work
many c o n f u s i n g r e s u l t
e v e n i n g s I have e n j o y e
B r i t a n n i c a . One day i t dawned on me t h a t the d i s t r i
b u t i o n of people i n the United S t a t e s versus other
a r e a s r e s e m b l e d t h e charge t r a n s f e r b e h a v i o r .
To
change t h i n g s t h e p e o p l e must move a r o u n d , get i n t o
and o u t o f c a r s , t r a i n s , p l a n e s .
What a memorable moment - t h e t h e o r y d i d not have
t o be a b s o l u t e l y r i g h t t o be u s e f u l i n g u i d i n g e x p e r
iments.
Why have I t a k e n such a c i r c u m s p e c t p a t h t o r e a c h
t h i s point? W e l l , I wish to present a c o n c e p t u a l i z a
t i o n o f t h e p r o b l e m s w h i c h has been u s e f u l t o me.
It
has h e l p e d t o b r i d g e t h e chasm s e p a r a t i n g d i f f e r e n t
experimental s i t u a t i o n s .
The f o l l o w i n g F i g u r e 8 i n d i c a t e s t h a t the l e c t u r e s
c o u l d be p l a c e d i n a v a r i e t y o f c a t e g o r i e s . F i r s t , the
f a m i l i a r m e t a l - e l e c t r o l y t e system w i t h gas e v o l u t i o n
p o t e n t i a l l y present.
Second, t h e systems i n v o l v i n g
m e t a l s s e p a r a t e d from the l i q u i d by a c o v e r i n g f i l m
s t r u c t u r e , and t h i r d t h e m e t a l s e p a r a t e d from a gas by
an i n t e r m e d i a t e phase l a y e r . There i s some a m b i g u i t y
e v i d e n t i n t h i s d e s c r i p t i o n ; however, i n t h e n e x t few
m i n u t e s p e r h a p s some new p e r s p e c t i v e s f o r t h o u g h t
o r g a n i z a t i o n can emerge.
I n a more g e n e r a l sense s u r f a c e c o r r o s i o n p r o
c e s s e s can be d e s c r i b e d i n terms o f the phases p r e s e n t
as shown i n F i g u r e 9.
Here t h e s o l i d i s n o t i d e n t i f i e d
s i m p l y as a m e t a l but a more g e n e r a l term S i s b e i n g
used w i t h L r e p r e s e n t i n g l i q u i d phase and G gas phase.
The systems l o c a l l y p r e s e n t can be r e p r e s e n t e d by t h e
n o t a t i o n s S - L , S - L - G , S-G or, i f a c o v e r i n g c h e m i c a l l y
a l t e r e d l a y e r e x i s t s on t h e s u r f a c e , then S i - S i s
present w i t h S i the s t a r t i n g m a t e r i a l .
2

12
CORROSION
CHEMISTRY
Solids
Ideally Perfect
R e a l i t y + I d e a l l y Imperfect
THEORY :
i f i t leads t o experiments
does n o t need t o be
RIGHT
t o be v e r y v a l u a b l e .
Figure 7.
Modeling

TUOMi
Corrosion:
Problem
of Materials
Science
Metal-Electrolyte-Gas
Metal-Solid-Liquid
Corrosion E l e c t r o chemistry
Iron D i s s o l u t i o n
Mechanisms
Corrosion I n h i b i t i o n
and I n h i b i t o r s
Stress Corrosion
Cracking
Solid Electrolyte-Ionic
E l e c t r o n i c Transport
Iron Passivation
Valve Metals D i e l e c t r i c
Layers
Treatments
LECTURE SERIES
CORROSION
Metal-Solid-Gas
High-Temperature
Corrosion
Low-Temperature
Atmospheric
Corrosion
C o r r o s i o n Phenomena
N o v e l Energy
Conversion Processes
Iron P a s s i v a t i o n
Figure 8.
Corrosion lecture classifications

14
CORROSION
CHEMISTRY
The p e r s p e c t i v e o f s i m p l e phases and phase e q u i l

i b r i a i s adequate f o r many c o r r o s i o n p r o b l e m s . T h i s i s
p a r t i c u l a r l y t r u e f o r the c a s e s where thermodynamic
f r e e energy d a t a r e a l l y d e s c r i b e what phases are p r e s e n t .
L e t us examine t h i s f o r a few m i n u t e s from the
viewpoint of everyday experience.
We w i l l u t i l i z e the
key d e v i c e w h i c h was r e s p o n s i b l e f o r our a r r i v a l a t
the l e c t u r e - t h e b l a c k box c a l l e d
THE
LEAD-ACID STORAGE BATTERY.
T h i s system p e r m i t s b r i e f d e s c r i p t i o n s o f some key

c o n c e p t s e n c o u n t e r e d i n c o r r o s i o n phenomena:
electrode
p o t e n t i a l s , exchange c u r r e n t s , mixed p o t e n t i a l s ,
c o r r o s i o n p o t e n t i a l s , p a s s i v e f i l m s , as w e l l as l e a d i n g
t o thermodynamic d e s c r i p t i o n s o f s y s t e m s .
The r e d o x systems o f t h e b a t t e r y a r e s i m p l y p r e
sented as:
Negative :
Anodic
Pb,
+ SO*
{ S )
PbS0iw
+ 2e
+ 0.335
( S }
Cathodic
Positive:
Pb0 , x + 4H
2
Pb
( s )
+Pb0
_
+ SO * + 2e
2 ( s )
+ 2 50>
2
Cathodic
?
PbSO* + 2 H 0
Anodic
2
PbSO^
( g )
+ 2H 0
2
1.685
^ 2
At the n e g a t i v e lead i s o x i d i z e d t o lead s u l f a t e d u r i n g

d i s c h a r g e w h i l e at the p o s i t i v e l e a d d i o x i d e i s
r e d u c e d t o l e a d s u l f a t e . The f u n c t i o n i n g o f the b a t
t e r y f o r many c y c l e s depends upon m a i n t a i n i n g the
reactions i s o l a t e d to t h e i r respective electrodes, to
h a v i n g the e l e c t r o n s f l o w i n g t h r o u g h an e x t e r n a l c i r
c u i t , and o n l y i o n i c c u r r e n t s f l o w i n g i n t h e i n t e r n a l
electrolyte circuit.
I f the p o t e n t i a l - c u r r e n t (E-i) c h a r a c t e r i s t i c s of
t h e i n d i v i d u a l r e a c t i o n s were measured, the r e a c t i o n s
c o u l d be r e a d i l y modeled as e l e c t r o c h e m i c a l r e a c t i o n s
w i t h t h e b a t t e r y a t open c i r c u i t as i n d i c a t e d by the
p r o c e s s e s i n F i g u r e 10.
I f dynamic e l e c t r o d e p o t e n t i a l c u r r e n t r e l a t i o n s h i p s were d e t e r m i n e d , t h e e l e c t r o d e i s
e x p e c t e d t o show t h e c l a s s i c T a f e l s l o p e b e h a v i o r s as
the exchange c u r r e n t o f the a n o d i c - c a t h o d i c e q u i l i b r i u m
i s s h i f t e d i n t o e i t h e r d i r e c t i o n . From t h e T a f e l
c u r v e s a v a l u e f o r t h e E and i o f the e l e c t r o d e
c o u l d be d e f i n e d .
Q

1.
Corrosion:
Problem
of Materials
15
Science
LOCAL REGION SOLID SURFACE TRANSFORMATIONS

Solid-Liquid
S-L
Solid 1-Solid 2-L
Solid-Liquid-Gas
S-L-G
S o l i d Gas
SG
S o l i d 1-Solid 2-L-G S o l i d 1-Solid 2-G
S i ~ S 2 """ L
Si
Figure 9.
Corrosion system
Pb0
+ 2H + H SO + 2e
2 ( s )
Positive
Pb0
2 ( s )
+2H +H SO
2
PbSOu
Potential
E
{s)
PbSOu
Anodic
l(
+2e -
+ 2 H 0
2
(s)
+ 2e - P b
( s )
+ SO,
Negative
Pb
( s )
S 0 ; - PbSO,
(s)
log i
Figure 10.
Model battery anodic-cathodic
reactions

+ 2e
16
CORROSION
CHEMISTRY
I f the two e l e c t r o d e s a r e s h o r t - c i r c u i t e d t o g e t h e r ,
t h e c a t h o d i c p r o c e s s o f t h e p o s i t i v e combines w i t h t h e
a n o d i c p r o c e s s o f the n e g a t i v e as shown i n F i g u r e 11.
The b a t t e r y now has a s i n g u l a r p o t e n t i a l - t h e s h o r t
circuited potential.
T h i s c l e a r l y i s a mixed p o t e n t i a l
o r c o u l d be v i e w e d as a c o r r o s i o n p o t e n t i a l o f the
system.
L o o k i n g a t F i g u r e 12, a s k e t c h o f a s i n g l e c e l l
shows t h a t t h e p o s i t i v e i s a p a s t e o f P b 0 i n a l e a d
grid.
T h i s e l e c t r o d e i n t h e e l e c t r o l y t e c l e a r l y must
have a mixed p o t e n t i a l s i n c e m e t a l l i c l e a d i n t h e
p r e s e n c e o f l e a d d i o x i d e and s u l f u r i c a c i d i s thermodynamically unstable.
At the n e g a t i v e the l e a d g r i d
contains pasted l e a d ! This i s a l s o unstable w i t h
respect to charging the b a t t e r y . Both e l e c t r o d e s
represent a c o r r o s i o n c o n t r o l problem!
Really, this i
the e l e c t r o d e s are f u l l
i n c r e a s e d so oxygen and hydrogen a r e e v o l v e d a t t h e
p o s i t i v e and n e g a t i v e , r e s p e c t i v e l y . T h i s i s i n d i
c a t e d by t h e p o t e n t i a l - l o g c u r r e n t l i n e s i n F i g u r e 13.
These r e a c t i o n s c o n v e r t t h e b a t t e r y i n t o a p o t e n t i a l
e x p l o s i v e by t h e H2-O2 r e c o m b i n a t i o n t o form w a t e r
i f a match i s used t o a i d i n s e e i n g how much w a t e r
needs t o be added. I f t h e 0 r e d u c t i o n c o u l d be made
t o p r o c e e d on t h e n e g a t i v e s u r f a c e as a l o c a l c o r r o
s i o n c u r r e n t , and i f t h e H c o u l d be made t o undergo
o x i d a t i o n on t h e p o s i t i v e s u r f a c e , a h e r m e t i c a l l y
s e a l e d c e l l c o u l d be made. These e l e c t r o c h e m i c a l
r e a c t i o n s , however, r e p r e s e n t forms o f l o c a l c e l l
r e a c t i o n s f a m i l i a r to c o r r o d i n g systems.
As any o f t h e s e r e a c t i o n s p r o c e e d a t t h e e l e c t r o d e
surface, the surface chemistry i s continuously changing.
The c o m p o s i t i o n o f t h e l o c a l e l e c t r o l y t e i n c o n t a c t
w i t h t h e s o l i d s i s c h a n g i n g . Thus, t h e s i m p l e chem
i s t r y i m p l i e d by t h e r e a c t i o n
2
Pb + P b 0
+ 2 H S0i> + PbSOi* + 2 0
2
r e a l l y does n o t e x i s t .
There a r e numerous changes o f
a complex form p r o c e e d i n g on t h e m e t a l s u r f a c e s , on
t h e m e t a l l i c h e a v i l y - d o p e d o x i d e P b 0 , on t h e PbSOi+
c r y s t a l l i t e s , on t h e Pb p a r t i c u l a t e s i n t h e n e g a t i v e
g r i d , as w e l l as i n systems o f g r a i n b o u n d a r i e s w h i c h
are present.
S u d d e n l y , as we p e e r beyond t h e c a s u a l s o l u t i o n
c h e m i s t r y e q u a t i o n , r a t h e r complex s o l i d s t a t e c h e m i s
t r y i s i n t e r a c t i n g w i t h s o l u t i o n and gas phases
processes.
2

Corrosion:
Figure 11.
Problem
of Materials
Science
Short circuit of battery terminals creates characteristic short circuit

potential (E ) and short circuit current (i ).
8C
8C

18
CORROSION
CHEMISTRY
LOAD
Pasted
Pb
Pasted
Pb0
|charge y-
dischargj
Pb
Grids
H0
2
Figure 12.
Simple cell in a lead-acid battery
V r
H 0
2 ( g )
Mg)
V)
+ 2 H
+2H + 2e+H
l
2e
Positive -
Mg) ^
(t)
Negative -
H2
* (g)
log i
Figure 13.
Hydrogen and oxygen evolution reactions at the battery electrode

1.
Corrosion:
Problem
of Materials
Science
19
C l e a r l y t h e system has e l e c t r o c h e m i c a l - c h e m i c a l
exchange c u r r e n t s a t t h e p o s i t i v e s and n e g a t i v e s w h i c h
d e f i n e t h e p o t e n t i a l s o b s e r v e d . The m e t a l g r i d must
show c o m b i n a t i o n s o f PbSOt* f i l m , P b 0 f i l m , as w e l l as
h y d r i d e f i l m phenomena. I s n ' t c o r r o s i o n c h e m i s t r y
e x c i t i n g i n t h a t b l a c k box under t h e hood?
The b a t t e r y e l e c t r o d e mixed p o t e n t i a l b r i n g s a t
t e n t i o n t o the c o r r o s i o n engineer's problem o f c o n t r o l
l i n g e i t h e r the cathodic or anodic process t o minimize
the c o r r o s i o n c u r r e n t . The problems o f s u r f a c e p a s s i
v a t i o n , the question of i d e n t i f y i n g the d i s t i n c t i v e
s p a t i a l l o c a t i o n s of the r e a c t i o n processes are
f r e q u e n t l y p r e s e n t i n p r a c t i c a l s i t u a t i o n s - what i s
c a t h o d i c t o an a n o d i c r e g i o n o r v i c e v e r s a , what a r e
u s e f u l ways t o m o d i f y t h e s u r f a c e p r o c e s s e s ?
Thus, when a t t e n t i o n i s g i v e n t o d e t a i l what
appeared as a s i m p l
l i t t l e t h o u g h t becom
F o r a few moments l e t ' s d r o p t h e key words and
turn t o c r e a t i n g a skeleton f o r the c o r r o s i o n engi
neer's interphase t r a n s p o r t processes.
We need a l l t h e
tools possible t o bring the materials science r e
s o u r c e s t o o u r a i d . How can we e x p r e s s q u e s t i o n s so
a i d can come from o t h e r e x p e r t s ?
2
Part I I
T h i s phase o f t h e d i s c u s s i o n i s c o n c e r n e d w i t h
concepts o f s o l i d s t a t e chemistry r a t h e r than a
d e t a i l e d a n a l y s i s o f a p a r t i c u l a r case.
The o b j e c t i v e
i s t o b r i n g a t t e n t i o n t o a v a r i e t y o f s u r f a c e chemis
t r y p e r s p e c t i v e s . T h i s v a r i e t y c a n be h e l p f u l because
t h e number o f ways we can scavenge i n f o r m a t i o n from
r e l a t e d m a t e r i a l s s c i e n c e a r e a s becomes expanded.
F u r t h e r , a v a r i e t y o f s e e m i n g l y u n c o n n e c t e d phenomena
can be b r o u g h t i n t o r e l a t e d b a l l g a m e s . The m u l t i d i s c i p l i n a r y character of r e a l material science i si t s
real richness.
E a r l i e r a t t e n t i o n was b r o u g h t t o t h e c o r r o s i o n
p r o c e s s e s o f l i q u i d - s o l i d systems. L e t ' s s t a r t w i t h a
m e t a l c o n t a c t i n g an e l e c t r o l y t e as do a l l e l e c t r o
chemistry t e x t s .
The s i m p l e s t model o f t h e e l e c t r i c a l d o u b l e l a y e r
between a m e t a l and an e l e c t r o l y t e i s t h e s i m p l e c a p a
c i t o r v i s u a l i z e d by Helmholtz- as shown i n F i g u r e 14.
The d i f f u s e i o n d i s t r i b u t i o n i n t h e l i q u i d phase was
r e c o g n i z e d by Gouy and Chapman^-' - t o form a space
charge r e g i o n a d j a c e n t t o t h e e l e c t r o d e s u r f a c e .
S t e r n ^ i n 1924 combined t h e s t r u c t u r e s t o form a
compact d o u b l e l a y e r a t t h e e l e c t r o d e s u r f a c e w i t h a
1

20
CORROSION
HELMHOLTZ
1879
fee
f
i'
\Helmholtz
Plane
. STERN (1924)
i l '
STERN-GRAHAME
imD
+4
Helmholtz Plane
Figure 14.
GOUY CHAPMAN
1910-1913
:*Outer Helmholtz Plane

Inner Helmholtz Plane
Modeh for the electrical double hyer at a metal surface

CHEMISTRY
1.
Corrosion:
Problem
of
Materials
21
Science
d i f f u s e space c h a r g e .
I n 1947 D a v i d Grahame added t o
t h i s t h e s p e c i f i c a d s o r p t i o n o f i o n s f o r m i n g an i n n e r
and o u t e r H e l m h o l t z p l a n e w i t h h y d r a t e d c a t i o n s not
a p p r o a c h i n g as c l o s e l y as t h e a n i o n s a t t h e i d e a l
metal substrate surface. In t h i s i d e a l p o l a r i z a b l e
e l e c t r o d e model p e r s p e c t i v e , no charge t r a n s f e r o c c u r s
between m e t a l and l i q u i d phase - i . e . , no F a r a d a i c
processes are present. I t i s important t o v i s u a l i z e
t h i s s u r f a c e r e g i o n as formed o f atoms, m o l e c u l e s , and
ions having s i g n i f i c a n t thermal v i b r a t i o n a l , r o t a t i o n a l
and t r a n s l a t i o n a l e n e r g y .
The s k e t c h e d s t r u c t u r e s a r e
f o r o n l y a moment i n t i m e b u t a r e a v e r a g i n g o v e r space
a d j a c e n t t o t h e e l e c t r o d e s u r f a c e when measurements
are b e i n g made.
A subsequent d e s c r i p t i o n by B o c k r i s and a s s o c i ates- - drew a t t e n t i o n t o f u r t h e r c o m p l e x i t i e s as shown
i n F i g u r e 15. The m e t a
combinations of o r i e n t e
s p e c i f i c a l l y adsorbed a n i o n s , f o l l o w e d by s e c o n d a r y
water d i p o l e s along w i t h the hydrated c a t i o n s t r u c t u r e s .
T h i s model s e r v e s t o b r i n g a t t e n t i o n t o t h e dynamic
s i t u a t i o n i n w h i c h changes i n p o t e n t i a l i n v o l v e
s e q u e n t i a l as w e l l as s i m u l t a n e o u s r e s p o n s e s o f molec
u l a r and a t o m i c systems a t and near an e l e c t r o d e s u r
f a c e . Changes i n p o t e n t i a l d i s t r i b u t i o n i n v o l v e i n t e r
a c t i o n s e x t e n d i n g from atom p o l a r i z a b i l i t y , t h r o u g h
d i p o l e o r i e n t a t i o n , t o i o n movements. The e l e c t r i c a l
f i e l d e f f e c t s a r e complex i n t h i s i d e a l p o l a r i z e d
e l e c t r o d e model.
The models c l e a r l y have n o t a s s i g n e d any a t o m i c
s t r u c t u r e t o the metal s i d e . With a m e t a l l i c s u b s t r a t e
R i c e , i n 1 9 2 8 , s h o w e d the e l e c t r i c f i e l d p e n e t r a t i o n
was i n d e e d s l i g h t .
C o n s e q u e n t l y , t h i s model was ade
quate f o r t h e i d e a l p o l a r i z a b l e e l e c t r o d e w i t h o u t
F a r a d a i c charge t r a n s f e r .
A f u r t h e r c o m p l i c a t i o n i s i n t r o d u c e d i n F i g u r e 16
where t h e p r e s e n c e o f s u r f a c e adatoms i s i n d i c a t e d as
w e l l as m e t a l l a t t i c e v a c a n c i e s i n t h e s u b s t r a t e
s u r f a c e . W i t h i n t h e system a t t e n t i o n now can be drawn
to F a r a d a i c processes i n v o l v i n g the s u b s t r a t e s t r u c t u r e .
The t r a n s f e r o f an atom t o t h e s u r f a c e can be e x p r e s s e d
by the e q u a t i o n
2
M/D
+ D
/ n
where M/Qs/
the s u r f a c e adatom, i s f u r t h e r p o t e n t i a l l y
i n v o l v e d i n t h e exchange p r o c e s s
M
/Q
+
s
M +
(H 0)
2
+ e +

22
CORROSION
Figure 16.
CHEMISTRY
Electrical double layer with structure introduced on the metal side

1.
TUOMi
Corrosion:
Problem
of Materials
Science
23
T h i s s u g g e s t s t h a t a t t e n t i o n needs t o be g i v e n t o
i n t e r p h a s e exchange c u r r e n t s w h i c h i n v o l v e n o t o n l y
e l e c t r o n t r a n s f e r from t h e m e t a l s u r f a c e , b u t may
i n v o l v e atom exchanges from t h e b u l k t o t h e s u r f a c e
r e g i o n . The p l a n e m e t a l s u r f a c e a s s o c i a t e d w i t h
s t u d y i n g t h e model i d e a l p o l a r i z e d e l e c t r o d e b e h a v i o r
now becomes p a r t o f an i n t e r p h a s e system s e p a r a t i n g
m e t a l from an e l e c t r o l y t e o r a gas phase system.
The e v o l u t i o n o f s e m i c o n d u c t o r e l e c t r o n i c s depen
ded upon d e v e l o p i n g a d e t a i l e d m a t e r i a l s s c i e n c e ,
f i r s t f o r germanium and t h e n f o r s i l i c o n .
This con
fronted the electrochemist w i t h a f u r t h e r refinement
o f t h e e l e c t r i c a l d o u b l e l a y e r systems model. A t t h e
surface of a s i l i c o n semiconductor c r y s t a l the e l e c
t r o n i c p r o c e s s now i s no l o n g e r s i m p l y an e l e c t r o n
t r a n s f e r from a m e t a l b u t i n v o l v e s two d i s t i n c t
reactants, electron
r e a c t i o n s are not equivalen
semiconductor, S :
1Si
S + OH"
>
S0H + e
S + OH" + > S0H

A f u r t h e r c o m p l i c a t i o n a r i s e s when a t t e n t i o n i s
f o c u s s e d on t h e e l e c t r o n d e n s i t y d i s t r i b u t i o n w i t h i n
the semiconductor s o l i d .
T h i s , i n c o n t r a s t t o the
m e t a l c a s e , now i s a b l e t o v a r y from a l o w t o a h i g h
c o n c e n t r a t i o n l e v e l as e l e c t r o n s i n a c o n d u c t i o n band
o r as h o l e s i n a v a l e n c e band. The e l e c t r i c f i e l d on
t h e s o l i d s i d e o f t h e e l e c t r i c a l d o u b l e l a y e r now has
s p a t i a l extent - a d i f f u s e double l a y e r character
exists w i t h i n the s o l i d .
The c o n v e n t i o n a l e l e c t r i c
f i e l d e f f e c t s p r e v i o u s l y a s s o c i a t e d w i t h i o n motion
and i o n d i s t r i b u t i o n s i n t h e e l e c t r o l y t e have a
c o u n t e r p a r t w i t h i n t h e s o l i d phase.
A f u r t h e r c o m p l i c a t i o n i s brought t o the f o r e
f r o n t by s i l i c o n - e l e c t r o l y t e e l e c t r o c h e m i c a l s t u d i e s .
T h i s i s t h e phenomena o f s u r f a c e s t a t e s a t t h e s o l i d e l e c t r o l y t e i n t e r f a c e . These become c r i t i c a l l y
i n v o l v e d i n c h a r g e t r a n s f e r r e a c t i o n s i n v o l v i n g com
p l e x r e a c t a n t s a t t h e s u r f a c e . Thus s i m p l e e l e c t r i c
f i e l d d i s t r i b u t i o n s are not present except i n p a r t i c
u l a r model c a s e s .
On t h e o t h e r hand, r a t h e r t h a n h a v i n g a semicon
d u c t o r r e p l a c i n g t h e m e t a l , t h e a c t u a l s i t u a t i o n may
i n v o l v e growth o f s e m i c o n d u c t o r l a y e r s on a m e t a l
s u r f a c e , o r a d i e l e c t r i c f i l m , o r more g e n e r a l l y a
compound MX s e p a r a t i n g t h e base m e t a l from t h e c o r r o
s i o n media. A new phase s e p a r a t e s t h e c o r r o d i n g base
from the r e a c t a n t s .

24
CORROSION
CHEMISTRY
The e x a m i n a t i o n o f t h e m a t e r i a l MX as a model twod i m e n s i o n a l l a t t i c e s o l i d phase, AB, i n F i g u r e 17 i s

r e v e a l i n g . The m a t e r i a l can have a v a r i e t y o f l a t t i c e
imperfection s t r u c t u r e s i n c l u d i n g
1 1
i n t e r s t i t i a l A and atoms
/,
/
i m p r o p e r s i t e A and atoms
A/G3,
B/CB
l a t t i c e v a c a n c i e s f o r A and s i t e s +1 > FT
a s s o c i a t e d A and v a c a n c i e s
1+1~1
as r e a d i l y d e s c r i b e d by a s i m p l i f i e d symbolism.
In
r e a l systems a t t e n t i o n must be g i v e n t o d e f i n i n g a t
l e a s t c o n c e p t u a l l y t h e n a t u r e o f t h e phases p r e s e n t .
F r e q u e n t l y , under o r d i n a r y c o n d i t i o n s the s o l i d does not
f i t any s i m p l e s t o i c h i o m e t r y o r e l e c t r i c a l n e u t r a l i t y
compound model but i s a s t r u c t u r e u n i q u e t o the a c t u a l
system under s t u d y .
from u n o r t h o d o x approache
I f a t t e n t i o n i s given to the combination of a
m e t a l M becoming c o v e r e d w i t h MX the model as shown i n
F i g u r e 18, s e v e r a l o b s e r v a t i o n s can be made as t o
i n t e r p h a s e systems and t h e growth o f t h e f i l m l a y e r .
At the e x t e r i o r s u r f a c e a p a r t i c u l a r combination of
i n t e r p h a s e exchange c u r r e n t s f o r s o l i d phase growth
can be f o r m u l a t e d depending on t h e d e t a i l e d c h a r a c t e r
of the s o l i d phase, the s u r f a c e s t a t e s , the allowed
e l e c t r o n i c processes.
S i m i l a r l y , a set of interphase
exchange c u r r e n t s can be f o r m u l a t e d a t t h e boundary o f
the m e t a l and t h e MX l a y e r a g a i n s u b j e c t t o c o n s t r a i n t s
d e f i n e d by t h e mass t r a n s p o r t p r o c e s s e s p e r m i s s i b l e i n
t h e c o v e r i n g l a y e r and i n t h e m e t a l .
The s i t u a t i o n i s i l l u s t r a t e d i n g r e a t e r d e t a i l i n
t h e f o l l o w i n g model s i t u a t i o n s where a t t e n t i o n i s g i v e n
t o t h e i n t e r p h a s e boundary exchange c u r r e n t s i n j e c t i n g
the l a t t i c e i m p e r f e c t i o n s which are r e s p o n s i b l e f o r
atom t r a n s p o r t t h r o u g h t h e compound MX A**
Thus i n F i g u r e 19 l a t t i c e v a c a n c y w i t h a t r a p p e d
h o l e i s i n j e c t e d a t t h e compound e l e c t r o l y t e i n t e r f a c e ,
t h e i m p e r f e c t i o n a t t h e metal-compound i n t e r f a c e r e a c t s
t o r e l e a s e a v a c a n c y i n t o the m e t a l .
Alternatively,
i n F i g u r e 20 t h e exchange p r o c e s s i n j e c t s a l a t t i c e
v a c a n c y on t h e c a t i o n l a t t i c e w h i c h a p p e a r s a t t h e
m e t a l compound i n t e r p h a s e t o r e l e a s e an e l e c t r o n and
t r a n s f e r a metal i o n i n t o the s u r f a c e r e g i o n .
T r a n s p o r t models such as t h e s e have been c r e a t e d
t o b r i n g a t t e n t i o n t o t h e p o s s i b i l i t y o f t h e boundary
exchange c u r r e n t s i n j e c t i n g i m p e r f e c t i o n i n t o a
c r y s t a l l i n e phase d u r i n g an a n o d i c p r o c e s s .
In f a c t ,
t h e y may d e t e r m i n e t h e s o l i d phase s t r u c t u r e s formed.
F u r t h e r m o r e , t h e m e t a l w i t h a s o l i d phase c o v e r i n g f i l m

1.
Corrosion:
Problem
of Materials
25
Science
B/n~
Journal of the Electrochemical Society
Figure 17.
A model two-dimensional AB compound lattice illustrating simple

imperfection structures expected as a systems variable (12)
ANION VACANCY
METAL ATOM VACANCY
CATION VACANCY
CATION
SURFACE SITE
AO-ATOMSr*y* AD-IONS
M
METAL
ANION
SURFACE SITE
SURFACE

Figure 18. Model situation where metal, M, is separated from corroding medium
by covering-layer compound (MX) containing imperfection structures (12)

26
CORROSION
CHEMISTRY
COMPOUND MX-ELECTROLYTE INTERFACE
Journal of the
Electrochemical Society
Figure 19. Model boundary
exchange currents involving the injec
tion of a lattice vacancy with trapped
hole at compound-electrolyte interface
and vacancy release into the metal with
a hole and metal ion in the compound
(12)
METAL
j
L
. | @ _ fe>
/ p/ j!g
D
|
COMPOUND
|
METAL COMPOUND
(g) I
g'
j __? I
! P/O^" D ; @
N
| @
COMPOUND MX- ELECTROLYTE INTERFACE
^g)

_ @ _ j
0~ D * ~ D | i
Journal of the
Electrochemical Society
Figure 20. Model boundary interphase
exchange currents involving httice vacancy injection at the compounds-electrolyte interface and vacancy exchange
into the metal releasing an electron and
transferring a metal ion into the compound hyer (12)
METAL
M
i
COMPOUND
MX
METAL COMPOUND
MX
M
(M)
_jgfc!
^


1.
Corrosion:
Problem
of
Materials
Science
27
can be i n r e v e r s i b l e e q u i l i b r i u m w i t h an e l e c t r o l y t e
w i t h o u t h a v i n g exposed m e t a l n e c e s s a r i l y i n c o n t a c t
w i t h an e l e c t r o l y t e . I n such a model, an i n c r e a s e i n
t h e d r i v i n g c u r r e n t s may i n c r e a s e the mass t r a n s p o r t
r a t e s ( a l t e r s o l i d phase s t r u c t u r e s ) w i t h i n l i m i t s so
t h e r a p i d phase t r a n s f o r m a t i o n s (M t o MX) can o c c u r
w i t h o u t n e c e s s a r i l y i n v o l v i n g i o n - s o l u t i o n and p r e c i p
i t a t i o n r e a c t i o n s i n t h e o r d i n a r y sense.
T h i s d i s c u s s i o n has b r o u g h t a t t e n t i o n t o t h e p o t
e n t i a l p r e s e n c e o f two c l a s s e s o f i n t e r p h a s e t r a n s p o r t
c o n d i t i o n s i n s o l i d s t a t e systems. L e t us examine
t h e s e f o r a moment f r o m t h e p e r s p e c t i v e o f f o r m i n g
s o l i d phases under model c o n d i t i o n s .
F o r t h e s i n g l e i n t e r p h a s e exchange p r o c e s s o f
s o l i d phase P2 i n t e r a c t i o n s w i t h P i shown i n F i g u r e 21,
a s e r i e s o f model c o n d i t i o n s a r e i l l u s t r a t e d
F o r each
a set of interphase
f o r m u l a t e d w h i c h hav
i n t e r p r e t a t i o n s . The f i r s t i s the l o c a l d e p o s i t i o n o f
m e t a l l i c t i t a n i u m by t h e t h e r m a l d e c o m p o s i t i o n o f T i C l i *
gas on a hot w i r e .
T h i s v a p o r p l a t i n g t e c h n i q u e can be
p e r f o r m e d t o grow a v a r i e d c r y s t a l l i t e s t r u c t u r e o f a
r e l a t i v e l y pure t i t a n i u m on t h e h o t f i l a m e n t . More
g e n e r a l l y , v a p o r p l a t i n g t e c h n i q u e s o f many complex
forms a r e used t o grow e p i t a x i a l s i l i c o n l a y e r s o f
c o n t r o l l e d impurity content onto s i l i c o n s u b s t r a t e s .
The c a r e f u l c o n t r o l o f c o n d i t i o n s r e s u l t s i n an amaz
i n g l y homogeneous f i l m growth o f h i g h s e m i c o n d u c t o r
q u a l i t y . The i m p e r f e c t i o n s t r u c t u r e i n a c o m p o s i t i o n
and s t r u c t u r a l sense depends on t e c h n i q u e d e t a i l s .
The second example i s e l e c t r o l y t i c p l a t i n g o f
copper f i l m s .
C o n t r a r y t o some e x p e c t a t i o n s growth
c l o s e t o e q u i l i b r i u m p o t e n t i a l c o n d i t i o n s does n o t
r e s u l t i n the h i g h e s t q u a l i t y d e p o s i t .
I n g e n e r a l , the
c o m p o s i t i o n and s t r u c t u r e o f the d e p o s i t depends on t h e
d e t a i l e d c o m b i n a t i o n o f t r a n s p o r t p r o c e s s e s towards and
away from t h e e l e c t r o d e s u r f a c e . A d d i n g t h e l o c a l
hydrodynamic v a r i a b l e s p r o v i d e s t h e system w i t h an
e x t r e m e l y b r o a d s t r u c t u r a l c h e m i c a l range.
The t h i r d example i n v o l v e s growth o f a c r y s t a l l i n e
s a l t phase from t h e s a t u r a t e d s o l u t i o n . The thermo
dynamic d e s c r i p t i o n a g a i n i s i n a d e q u a t e f o r d e s c r i b i n g
the d e t a i l e d s t a t e s of the s o l i d .
The r e l a t i v e l y
anhydrous c h l o r i d e i o n r e a d i l y d e p o s i t s i n t o the
s u r f a c e l a t t i c e but t h e sodium i o n must be d e h y d r a t e d
t o form N a C l . T h i s means t h a t w a t e r must be d i f f u s e d
away from t h e s u r f a c e d u r i n g s o l i d i f i c a t i o n .
The w h i t e
c a s t o f s a l t , termed v e i l i n g , i n v o l v e s s o l u t i o n i n c o r
p o r a t i o n d u r i n g growth w i t h a subsequent d i f f u s i o n o f
t h e s o l v e n t o u t o f the c r y s t a l .

28
CORROSION
CHEMISTRY
IP
Substrate
Pi
2
Filament
S2
Pi
+ +
Fe
Cu
Seed
Crystal
Na
CI
Seed
Crystal
Ge
Cu
Plating
Solution
Saturated
NaCl
Electrolytic
Plating
Solution
Precipitation
Molten
Ge
Solidification
of Melt
\
Figure 21.
Single interphase exchange current model for solid-phase formation

(P ) through interphase reactions with second phase (Pi)
2

1.
Corrosion:
Problem
of
Materials
Science
29
The f o u r t h example i s t h e c o n t r o l l e d s o l i d i f i c a
t i o n o f germanium (or s i l i c o n ) t o produce s e m i c o n d u c t o r
grade m a t e r i a l s . The s o l i d phase s t r u c t u r e and compo
s i t i o n depend s t r o n g l y upon the i n t e r p h a s e exchange
p r o c e s s e s w h i c h can enhance i n c o r p o r a t i o n i n t o the
s o l i d o r i n t o t h e l i q u i d d e p e n d i n g upon ???
This
example i m p l i c i t l y i n c l u d e s t h e p r o d u c t i o n o f most o f
the m e t a l l i c s t r u c t u r a l m a t e r i a l s .
The m e t a l a l l o y systems g e n e r a l l y have b o t h c o n
t r o l l e d and u n c o n t r o l l e d i m p u r i t i e s b e i n g d e p o s i t e d and
r e d i s t r i b u t e d w i t h i n the s o l i d as a r e s u l t o f complex
l i q u i d hydrodynamic i n t e r p h a s e r e g i o n p r o c e s s e s as w e l l
as s e c o n d a r y s o l i d s t a t e d i f f u s i o n and t r a n s f o r m a t i o n
processes.
This materials science i s f a m i l i a r to a l l
c o r r o s i o n e n g i n e e r s who become i n v o l v e d w i t h c o m m e r c i a l
systems.
The second i n t e r p h a s
t h e dynamic i n t e r a c t i o
phase exchange c u r r e n t s a t t h e s e p a r a t e d b o u n d a r i e s as
i n d i c a t e d i n F i g u r e 22 where a s o l i d phase P i s formed
by i n t e r a c t i o n s i n v o l v i n g the s e p a r a t e d phases P
and
Pi.
The c l a s s i c o x i d a t i o n o f aluminum t o form a p a s s
i v e s u r f a c e i s the f i r s t i l l u s t r a t i o n .
While the
second model i s t h e a n o d i c o x i d a t i o n o f aluminum, the
i n t e r p h a s e t r a n s p o r t phenomena h e r e can be d i s t r i b u t e d
w i t h i n more complex c o n t e x t s as a r e s u l t o f the
boundary l a y e r c o m p o s i t i o n changes i n the e l e c t r o l y t e .
T h i s model i s a p a r t i c u l a r l y f a s c i n a t i n g one because
s e v e r a l decades ago i t was c l e a r t h a t t h e l a r g e
n e g a t i v e l y c h a r g e d oxygen a n i o n c o u l d n o t m i g r a t e i n
such o x i d a t i o n p r o c e s s e s - the m e t a l i o n +3 aluminum
was s m a l l and o f c o u r s e had t o t r a n s p o r t a l l t h e
current through the f i l m .
Famous l a s t words t h a t
c r e a t e d a c r i s i s when good t r a n s p o r t number e x p e r i m e n t s
were p e r f o r m e d w h i c h showed b o t h atoms move i n the
film-forming process
The s i l v e r t a r n i s h i n g r e a c t i o n i n v o l v i n g hydrogen
s u l f i d e i s a c l a s s i c of s o l i d s t a t e m a t e r i a l s science
l i t e r a t u r e , and the z i n c o x i d a t i o n i s y e t a n o t h e r
example o f a more complex p r o t e c t i v e l a y e r c o r r o s i o n
p r o b l e m f o r w h i c h wide r a n g e s o f d a t a e x i s t r e l a t i n g
to p u r i t y , to k i n e t i c c o n d i t i o n s , etc.
T h i s i n t e r p h a s e exchange c u r r e n t m o d e l i n g o f the
s o l i d phase f o r m a t i o n p r o c e s s s e r v e s t o emphasize the
v a r i e d p e r s p e c t i v e s from w h i c h u s e f u l i n f o r m a t i o n can
be drawn t o a i d i n d e s c r i b i n g and u n d e r s t a n d i n g c o r r o
s i o n p r o c e s s e s i n v a r i e d systems. R a r e l y are the r e a l
systems s i m p l e and many p i e c e s o f d a t a a r e examined
b e f o r e t h e models do i n c o r p o r a t e t h e f u l l ranges of
2

CORROSION
IP
CHEMISTRY
IP
2-3
1-2
- S:
Al
gas
j
Al
lAnodic
Oxide
Ag
Ag S
2
Anodizing
Electrolyte
}
H2S
Tarnishing
1
Zn
ZnO
Alkaline
Electrolyte
- -
Figure 22.
Passivation
II
(capacitors)
Battery
Reaction
Double interphase exchange current model for solid-phase formation

2
s and P2-Pi boundaries
(P ) through interphase reactions (IP) at P -P

2

1.
Corrosion:
Problem
of
Materials
31
Science
variables present.
The c o r r o s i o n e n g i n e e r ' s e x p e r i e n c e s e x i s t i n a
complex s y n e r g i s t i c r e l a t i o n s h i p t o t h e v a r i e d i n t e r
phase exchange c u r r e n t r e l a t i o n s h i p s p r e s e n t w i t h i n
systems o f p r a c t i c a l c o n c e r n . I t i s i n d e e d r a r e t h a t
h i s problems a r e e x p r e s s e d w i t h i n any model m a t e r i a l s
science contexts.
He must n e c e s s a r i l y work w i t h the
e c o n o m i c a l l y f e a s i b l e m a t e r i a l s f o r the p r a c t i c a l
a p p l i c a t i o n s . As t h e p r o d u c t i o n e n g i n e e r s work w i t h
s t e a d i l y i n c r e a s i n g l a b o r c o s t s i n a s s e m b l y , the
m a t e r i a l s e n g i n e e r - c o r r o s i o n e n g i n e e r - wear e n g i n e e r
become i n c r e a s i n g l y on t h e s p o t t o e x t r a c t t h e r e q u i r e d
v a l u e s from cheaper m a t e r i a l s .
I t i s no j o k e t h a t
the c o n t r a c t went t o t h e l o w e s t b i d d e r .
What does t h i s mean t o a l l o f us assembled h e r e ?
F i r s t , a r e c o g n i t i o n needs t o e x i s t t h a t i n a l l
practical situation
b a l l game - i t canno
i f we are e x p e c t e d t o w a r r a n t y t h e p e r f o r m a n c e .
Second, a r e c o g n i t i o n needs t o e x i s t t h a t , though
the problems a r e complex, many new t o o l s and s k i l l s
a r e i n c r e a s i n g l y a v a i l a b l e t o c l a r i f y d i r e c t l y the
c h a r a c t e r o f t h e problems p r e s e n t . The a r t i c l e s w h i c h
follow bring attention to t h i s .
T h i r d , a r e c o g n i t i o n needs t o e x i s t t h a t o r g a n
i z e d knowledge on s o l i d s t a t e c h e m i s t r y i s becoming
i n c r e a s i n g l y a v a i l a b l e t o us.
T h i s i s i l l u s t r a t e d by
. . Hannay's m u l t i - v o l u m e T r e a t i s e on S o l i d S t a t e
C h e m i s t r y . - ^ As n o t e d by Hannay i n h i s f o r e w o r d ,
"... Yet even though the r o l e o f c h e m i s t r y
i n t h e s o l i d s t a t e s c i e n c e s has been a v i t a l
one and t h e s o l i d s t a t e s c i e n c e s have, i n
t u r n , made enormous c o n t r i b u t i o n s t o chemi
c a l t h o u g h t , s o l i d s t a t e c h e m i s t r y has not
been r e c o g n i z e d by t h e g e n e r a l body o f
c h e m i s t s as a major s u b f i e l d o f c h e m i s t r y ...
S o l i d s t a t e c h e m i s t r y has many f a c e t s , and
one o f t h e p u r p o s e s o f t h i s t r e a t i s e i s t o
help d e f i n e the f i e l d . "
I f c h e m i s t s are t o be t h e a t o m i c - m o l e c u l a r domain
custodians of s o l i d s t a t e m a t e r i a l s science, a serious
c o n c e r n w i l l need t o e x i s t f o r a c q u i r i n g u s e f u l b a c k
grounds i n t h i s a r e a .
A s i g n i f i c a n t related publica
t i o n i s t h e r e c e n t appearance o f F. A. K r o g e r s second
e d i t i o n of the Chemistry of Imperfect C r y s t a l s - i n
t h r e e volumes. The d e f e c t c h e m i s t r y c o n c e p t s from t h i s
a r e a need t o be i n c o r p o r a t e d more g e n e r a l l y i n t o the
new s u r f a c e s c i e n c e w h i c h r e l a t e s t o t h e e n v i r o n m e n t a l
1
1 5

32
CORROSION
CHEMISTRY
s t a b i l i t y of materials.
F o u r t h and l a s t , b u t n o t l e a s t , a g r o w i n g r e c o g n i t i o n needs t o e x i s t t h a t the a p p l i c a t i o n o f the new
complex i n s t r u m e n t a l t e c h n i q u e s can c l a r i f y the s u r face chemistry s p e c u l a t i o n s p r e v i o u s l y necessary.
So
f r e q u e n t l y our c o n c e p t u a l i z a t i o n s o f the r e a l p r o b l e m
a r e wrong. I p e r s o n a l l y a c c e p t t h e h y p o t h e s i s t h a t
t h e f i r s t s i x models when t e s t e d i n d e t a i l w i l l p r o v e
wrong. However, as t h e r e a l model emerges i n i t s
complex beauty, t h e number o f p a t h s t o o p t i m i z a t i o n s
have m u l t i p l i e d and s c i e n c e i s no l o n g e r dead ended.
The complex i n s t r u m e n t a t i o n s i n c l u d e LEED, low
energy e l e c t r o n d i f f r a c t i o n , w h i c h i s r e v e a l i n g a
complex model f o r s u r f a c e s t r u c t u r e when a p p a r e n t
m u l t i l a y e r a d s o r p t i o n o f oxygen p r o c e e d s on c l e a n m e t a l
surfaces.
It also include
chemical a n a l y s i s ,
t h a t can p r o v e t h a t t h e p o s t u l a t e d c o v e r i n g f i l m , by
g o l l y , i s n o t c o v e r i n g , and what's the s u r f a c e compos i t i o n ? E v e r t r y t o d e a l w i t h n i n e s u r f a c e components
a t once? W e l l , you can s e r i o u s l y e x p l o r e t h a t d i s t r i b u t i o n f o r e l e c t r o l e s s n i c k e l f i l m s b e i n g d e p o s i t e d on
a catalyzed substrate.
I t a l s o i n c l u d e s Auger e l e c t r o n s p e c t r o s c o p y
microprobe i d e n t i f i c a t i o n of the surface crud i n the
p i t , or d e f i n i t i o n of the surface composition g r a d i e n t
p r e v i o u s l y o m i t t e d from t h e s p e c u l a t i o n on atom
transport processes.
The s c a n n i n g e l e c t r o n m i c r o s c o p e p r o v i d e s us
neophytes w i t h a r e a l i s t i c l o o k a t s u r f a c e s t r u c t u r e
as e n c o u n t e r e d i n t h e system. When teamed w i t h Auger
o r ESCA a c o n f r o n t a t i o n can be c r e a t e d w i t h s e l f ,
t r y i n g t o r a t i o n a l i z e the o l d c o m f o r t a b l e models t h a t
d i d n o t have t o acknowledge t h a t s u r f a c e c h e m i c a l
s t r u c t u r e r e a l l y e x i s t e d on t h e " p o l y p h a s e inhomogeneous s o l i d c o n t a i n i n g h e t e r o g e n e i t y homogeneously
dispersed."
C o r r o s i o n i s h e r e t o s t a y . The wedding t o
m a t e r i a l s s c i e n c e i s i m p l i c i t l y r e v i e w e d i n the f i r s t
five figures.
I t i s a c l e a r l y i m p o r t a n t complex m a t e r i a l s s c i e n c e d r a w i n g on a l l t h e o t h e r d i s c i p l i n e s .
As
t h e s u r f a c e s c i e n c e o f i n t e r p h a s e mass and charge
t r a n s p o r t phenomena on s o l i d s c o n t i n u e s t o e v o l v e t h e n
more c l e a r l y , d e f i n e d new r o u t e s f o r p r o d u c t o p t i m i z a t i o n s w i l l be e v i d e n t .
Would you agree t h a t c o r r o s i o n i s t h e most g e n e r a l
problem o f m a t e r i a l s s c i e n c e ?
May a l l have f u n e x p l o r i n g t h e new v i s t a s o f our
p h y s i c a l world through the f o l l o w i n g c h a p t e r s .
For

01.
Corrosion: Problem of Materials Science
33
indeed we are a l l stewards of the u t i l i z a t i o n of mater

i a l s on t h i s scene i n s e r v i c e to a l l . May the mastery
of c o r r o s i o n extend the resources a v a i l a b l e to a l l
those who w i l l c e l e b r a t e the t r i c e n t e n n i a l , for few of
us w i l l have t h i s p r i v i l e g e .
Acknowledgements
I would l i k e to s p e c i f i c a l l y acknowledge the c h a l
lenge provided by Dr. Rudolph Hausler when he i n d i c a t e d
that preparing the overview would be an easy t a s k .
It
wasn't, but i t d i d provide an opportunity to survey
c o r r o s i o n l i t e r a t u r e and to recognize more f u l l y the
t i t l e of t h i s a r t i c l e : Corrosion (is) the Most General
Problem of M a t e r i a l s Science.
General
References
1.
Tedmon, C r a i g S . , e d i t o r , "Corrosion Problems i n

Energy Conversion and Generation," Corrosion D i v
ision,
E l e c t r o c h e m i c a l Society (1974).
2. Evans, U. R . , "Corrosion and Oxidation of M e t a l s :
Scientific
P r i n c i p l e s and P r a c t i c a l A p p l i c a t i o n s , "
A r n o l d , London (1960).
3. Fontana, M. G., Greene, N . D . , "Corrosion Engin
e e r i n g , " M c G r a w - H i l l , New York (1967).
4. Hauffe, ., "Oxidation of M e t a l s , " Plenum Press,
New York (1965).
5. Hamner, . E., compiler, "Corrosion Data Survey:
Metals and Non-Metals," Fifth E d i t i o n , N a t i o n a l
A s s o c i a t i o n of Corrosion Engineers, Houston,
Texas (1974).
6. Nathan, C. C . , e d i t o r , "Corrosion I n h i b i t o r s , "
N a t i o n a l A s s o c i a t i o n of Corrosion Engineers,
Houston, Texas (1973).
7. Pourbaix, ., "Lectures on Electrochemical C o r r
o s i o n , " Plenum Press, New York (1973).
8. U h l i g , . . , "Corrosion and Corrosion C o n t r o l :
An I n t r o d u c t i o n to Corrosion Science and Engin
e e r i n g , " John Wiley, New York (1963).
9. U h l i g , H. H., et. al., "Corrosion Handbook," W i l e y ,
New York, (1948).
10. " C o r r o s i o n , the Journal of Science and Engineering,"
published monthly by the N a t i o n a l A s s o c i a t i o n of
Corrosion Engineers, Houston, Texas.

CORROSION CHEMISTRY
34
Literature Cited
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
General References
1-10.
Stern, M . , et. al., J . Electrochem. Soc. (1957)
104 pp. 56-63, 559-63, 645-50.
Helmholtz, H . , Wiss Abhandlphysik. Tech. Reichenstalt I (1879) p. 925.
Gouy, G . , J. Phys. (1910) 9 p. 457.
Chapman, D. L., P h i l . Mag. (1913) 25 (6) p. 475.
Stern, ., z. Electrochem. (1924) 30 p. 508.
Grahame, D. C . , Chem. Rev. (1947) 41 p. 441.
Bockris, J . O'M., et. al., Proc. Roy. Soc.
(1963) A274 pp. 55-79.
Rice, . K . , Phys. Rev. (1928) 31 p. 1051,
MacDonald, J . R., J. Appl. Phys. (1964) 35 (10)
p. 3053.
See, for exampl
381-4 08, "The
Semiconductors," H. C. Gatos, editor, John Wiley,
New York (1960).
Rees, A. L. G . , "Chemistry of the Defect Solid
State," John Wiley, New York (1954).
Croft, G. T., and Tuomi, D., J. Electrochem.
Soc. (1961) 108 p. 915.
Davies, J. . , et. al., J. Electrochem. Soc.
(1965) 112 p. 675.
Hannay, . . , editor, "Treatise on Solid State
Chemistry," Volumes 1-7, Plenum Press, New York
(1974).
Kroger, F. . , "Chemistry of Imperfect Crystals Volume 1, Preparation, Purification, Crystal
Growth, and Phase Theory; Volume 2, Imperfection
Chemistry of Crystalline Solids; Volume 3,
Applications of Imperfection Chemistry: Solid
State Reactions and Electrochemistry," North
Holland-American Elsevier, New York (1974).
RECEIVED
September 1, 1978.

2
Electrochemical Techniques in C o r r o s i o n Studies
FRANCIS M. DONAHUE
Department of Chemical Engineering, University of Michigan, Ann Arbor, MI 48109
Corrosion may be defined as the spontaneous de

terioration
of a s t r u c t u r e or part of a s t r u c t u r e due
to the a c t i o n of th
environmental agents
the s t r u c t u r e is assumed to be m e t a l l i c and the en
vironment is assumed to be aqueous. Using t h i s
defini
tion and the c o n s t r a i n t s noted, t h i s chapter will out
line the e l e c t r o c h e m i c a l techniques used to develop
criteria
of c o r r o s i o n and those used in the study of
corrosion
kinetics.
Chemical
Criterion
of Corrosion
Free Enthalpy Change.

In the definition of c o r r o s i o n given above, the
word "spontaneous" was used in the thermodynamic sense,
i.e.,
a chemical r e a c t i o n for which the free enthalpy
change, G, is negative. Therefore, one can a s c e r t a i n
whether a postulated c o r r o s i o n r e a c t i o n can lead to
c o r r o s i o n by determining the s i g n of the free enthalpy
change of the r e a c t i o n .
The free enthalpy change for a chemical r e a c t i o n
at a temperature, T, is given by
AG = AG + RT n ( n ( a )
T
(1)
where AG is the standard free enthalpy change for the

r e a c t i o n at the prescribed temperature, is the m u l t i
p l i c a t i o n operator, a and are the a c t i v i t y (fugac i t y , for gaseous species) and s t o i c h i o m e t r i c c o e f f i c
i e n t , r e s p e c t i v e l y , for a s p e c i e s , Y , in the chemical
r e a c t i o n and R is the gas constant. By convention,
Y
0-8412-0471-3/79/47-089-035$10.25/0

36
CORROSION
CHEMISTRY
stoichiometric c o e f f i c i e n t s f o r reactants are negative

w h i l e those f o r p r o d u c t s a r e p o s i t i v e .
The s t a n d a r d f r e e e n t h a l p y change f o r a c h e m i c a l
r e a c t i o n can be c a l c u l a t e d from t a b u l a t e d v a l u e s o f
v a r i o u s thermodynamic f u n c t i o n s (1-3J. F o r aqueous
c h e m i c a l r e a c t i o n s at 25C., t h e s t a n d a r d f r e e e n t h a l p y
change is computed from
A G
298 =
( 2 )
where is t h e summation o p e r a t o r and is t h e s t a n d

ard c h e m i c a l p o t e n t i a l o f a s p e c i e s , Y, at 25C.
P o u r b a i x {!_) has t a b u l a t e d t h e s t a n d a r d c h e m i c a l p o t e n
t i a l s o f most s p e c i e s o f i n t e r e s t in c o r r o s i o n s t u d i e s .
A t o t h e r temperatures, t h e s t a n d a r d f r e e e n t h a l p y
change is
AG*
= ( ^
9 8
+ TEv ((G-H- )/T)

Y
9 8
(3)
where H
is
the standard enthalpy o f formation
of a s p e c i e s , Y, at 25C and ( ( G - H ) / T ) is a
thermodynamic f u n c t i o n which depends on t h e s p e c i e s , Y,
and t h e temperature, T. These thermodynamic q u a n t i t i e s
are t a b u l a t e d in some r e f e r e n c e books (2^3J .
E q u a t i o n 1 is u s e f u l as a c r i t e r i o n o f c o r r o s i o n
f o r p o s t u l a t e d c o r r o s i o n r e a c t i o n s . I t s main u t i l i t y
is t h a t i t p e r m i t s one t o a s c e r t a i n whether a p a r t i c u
l a r e n v i r o n m e n t a l agent ( d i s s o l v e d s p e c i e s ) o r t h e
s o l v e n t can i n t e r a c t c h e m i c a l l y w i t h t h e m e t a l l i c
s t r u c t u r e t o cause c o r r o s i o n o f t h e s t r u c t u r e . I f t h e
computed f r e e e n t h a l p y change is p o s i t i v e , i t i n d i c a t e s
t h a t c o r r o s i o n cannot o c c u r by t h e p o s t u l a t e d r e a c t i o n .
However, i t does n o t mean t h a t c o r r o s i o n cannot o c c u r
due t o t h e a c t i o n o f another e n v i r o n m e n t a l agent.
T h e r e f o r e , computations o f t h i s s o r t s h o u l d be exhaust
i v e and account f o r a l l e n v i r o n m e n t a l a g e n t s . I f t h e
computed f r e e e n t h a l p y change is n e g a t i v e , i t i n d i c a t e s
t h a t c o r r o s i o n by t h e p o s t u l a t e d r e a c t i o n is p o s s i b l e .
The computation p r o v i d e s no i n f o r m a t i o n about t h e r a t e
of t h e c o r r o s i o n r e a c t i o n .
Many c o r r o s i o n p r o c e s s e s , e.g., s t r e s s c o r r o s i o n
c r a c k i n g and o t h e r c o r r o s i o n - f r a c t u r e p r o c e s s e s , cannot
be d e s c r i b e d c o m p l e t e l y by a c h e m i c a l r e a c t i o n . These
p r o c e s s e s a r e complex i n t e r a c t i o n s among c h e m i s t r y ,
p h y s i c a l p r o p e r t i e s o f t h e m e t a l and m e c h a n i c a l s t r e s s .
T h e r e f o r e , t h e c o r r o s i o n tendency o f t h e m e t a l - e n v i r o n
ment i n t e r a c t i o n cannot be e v a l u a t e d u s i n g E q u a t i o n 1.
A t t h e p r e s e n t time, e m p i r i c a l c r i t e r i a (which a r e be
yond t h e scope o f t h i s c h a p t e r ) a r e used.
8

Electrochemical
D O N A H U E
Techniques
I l l u s t r a t i o n 1. C h e m i c a l C r i t e r i o n o f C o r r o s i o n .
Copper m e t a l is in c o n t a c t w i t h a s t r o n g a c i d
s o l u t i o n at 25C.
a) I f t h e o n l y i n f o r m a t i o n a v a i l a b l e a r e t h e
a c t i v i t i e s o f - h y d r o g e n i o n (10
) and c u p r i c i o n (10~ ) , can c o r r o s i o n o c c u r ?
b) I f oxygen at a f u g a c i t y o f 0.2 is in e q u i
l i b r i u m w i t h t h e s o l u t i o n in p a r t " a " ,
can c o r r o s i o n o c c g r ?
_
c) I f f e r r o u s (a=10
) and f e r r i c (a=10
)
i o n s a r e c o n t a m i n a n t s o f t h e s o l u t i o n in
p a r t " a " , can c o r r o s i o n o c c u r ?
Solutions :
a) Assume a c o r r o s i o
reaction
Cu + 2 H >
From P o u r b a i x (1) and i n s p e c t i o n o f
chemical r e a c t i o n ,
Y
Species
(kcal/mole)
Y
Cu
0
-1
H
0
-2
the
Cu
H
2 +
15.53
0
+1
+1
U s i n g E q u a t i o n s 1 and 2 and the a v a i l a b l e

d a t a (assuming u n i t f u g a c i t y f o r hydrogen
gas) ,
AG = (-1) (0) + (-2) (0) + (1) (15530) + (1) (0)
+
(1.987) (298)
n( ( 1 0
- 4
)/(10~ ) )
= +1.553X10 c a l / m o l e o f Cu
T h e r e f o r e , c o r r o s i o n c a n n o t o c c u r by
postulated reaction.
b) Assume a c o r r o s i o n r e a c t i o n ,
2Cu
+ 4H
+ 0
-> 2 C u
2 +
From P o u r b a i x (1) and

Species
Cu
Cu
H0
2
+ 2H 0
2
i n s p e c t i o n of
0
0
2 +
the
(kcal/mole)
0
H
2
the
15.53
-56.69
Y
-2
-4
1
+2
+2

38
CORROSION
CHEMISTRY
U s i n g E q u a t i o n s 1 and 2 and t h e a v a i l a b l e
d a t a (assuming u n i t a c t i v i t y f o r w a t e r ) ,
AG = (-2) (0) + (-4) (0) + (-1) (0) +
(2) (15530) + (2) (-56690) +
(1.987) (298) n((10~ ) /(10~ ) (0.2)
4
= -8.14X10 c a l / 2 mole o f Cu
T h e r e f o r e , c o r r o s i o n can o c c u r as a r e s u l t
of the p o s t u l a t e d r e a c t i o n .
c) Assume a c o r r o s i o n r e a c t i o n ,
3+
2+
2+
Cu + 2Fe
+ Cu
+ 2Fe
From P o u r b a i x (1) and i n s p e c t i o n o f t h e
z
Species
(kcal/mole)
Y
Cu
0
1
3+
Fe
-2.5
Cu
15.53
+1
Fe
-20.30
+2
U s i n g E q u a t i o n s 1 and 2 and t h e a v a i l a b l e
data,
AG = (-1) (0) + (-2) (-2530) + (1) (15530)
2 +
2 +
(2) (-20300) + (1.987) (298)
n(10" )
= -2.27X10 c a l / m o l e o f Cu
T h e r e f o r e , c o r r o s i o n can o c c u r by t h e p o s t ulated reaction.
E l e c t r o c h e m i c a l Thermodynamics
E l e c t r o d e P o t e n t i a l Measurements.
E l e c t r o c h e m i c a l r e a c t i o n s can be w r i t t e n in t h e
g e n e r a l form
Red = Ox + ne"
(4)
where Red r e p r e s e n t s t h e reduced form o f a c h e m i c a l

s p e c i e s (and any o t h e r s p e c i e s w i t h w h i c h i t r e a c t s in
t h e e l e c t r o c h e m i c a l r e a c t i o n ) , Ox r e p r e s e n t s t h e o x i
d i z e d form o f t h e same c h e m i c a l s p e c i e s (and any o t h e r
s p e c i e s w i t h w h i c h i t r e a c t s ) and is t h e s t o i c h i o
m e t r i c c o e f f i c i e n t o f t h e e l e c t r o n , e~. E l e c t r o c h e m i c a l
r e a c t i o n s t a k e p l a c e at t h e i n t e r f a c e between a m e t a l
(or o t h e r e l e c t r i c a l l y c o n d u c t i v e s u b s t r a t e ) and a
s o l u t i o n . An e l e c t r i c f i e l d e x i s t s a c r o s s t h i s m e t a l s o l u t i o n i n t e r f a c e due t o t h e n a t u r e o f t h e r e a c t i o n

2.
Electrochemical
D O N A H U E
Techniques
39
and t h e d i s p o s i t i o n o f i o n i c and d i p o l a r s p e c i e s on
the s o l u t i o n s i d e o f t h e i n t e r f a c e . Although t h i s
e l e c t r i c f i e l d is p r e s e n t , i t c a n n o t be measured d i
r e c t l y . I n s t e a d , a r e l a t i v e measurement is made w h i c h
provides u s e f u l information.
The c i r c u i t used in t h i s measurement is shown in
F i g u r e 1. The e l e c t r o d e under i n v e s t i g a t i o n , TE, is
c o n n e c t e d t o a second e l e c t r o d e , RE, by means o f a
v o l t a g e - m e a s u r i n g d e v i c e , E. S i n c e i t is n e c e s s a r y t o
make t h e s e measurements in t h e v i r t u a l absence o f a
c u r r e n t f l o w i n g in t h e c i r c u i t , t h e v o l t a g e - m e a s u r i n g
d e v i c e s h o u l d p o s s e s s a l a r g e (>10^ ohms) i n p u t imped
ance. I n a d d i t i o n , i t is u s u a l l y n e c e s s a r y t o make
measurements o v e r t h e range o f 2.0V w i t h an a c c u r a c y
on t h e o r d e r o f lmV.
The r e f e r e n c e e l e c t r o d e , RE, s h o u l d p o s s e s s a
s t a b l e , known e l e c t r o d
t h e e l e c t r i c f i e l d at
S i n c e a l l e l e c t r o d e p o t e n t i a l measurements a r e r e l a t i v e ,
i t is c o n v e n i e n t t o have an " u l t i m a t e r e f e r e n c e p o i n t " .
By c o n v e n t i o n , t h e e l e c t r o d e p o t e n t i a l o f t h e hydrogenhydrogen i o n e l e c t r o c h e m i c a l r e a c t i o n , i . e . ,
H
= 2H
+ 2e"~
(5)
is assumed t o have a v a l u e o f 0.000V when hydrogen gas

is at u n i t f u g a c i t y and t h e hydrogen i o n is at u n i t
a c t i v i t y . T h i s is t h e s o - c a l l e d s t a n d a r d hydrogen
e l e c t r o d e (SHE). The e l e c t r o d e p o t e n t i a l s o f some
common r e f e r e n c e e l e c t r o d e s ( r e l a t i v e t o t h e e l e c t r o d e
p o t e n t i a l o f SHE) a r e g i v e n in T a b l e I .
The e l e c t r o d e p o t e n t i a l o f t h e t e s t e l e c t r o d e , TE,
shown in F i g u r e 1 is t h e v o l t a g e measured on t h e
d e v i c e , , and is r e p o r t e d as "x.xxxV v s . RE". I f i t
is n e c e s s a r y t o c o n v e r t t h e v a l u e o f t h e e l e c t r o d e
p o t e n t i a l o f a t e s t e l e c t r o d e from one r e f e r e n c e
e l e c t r o d e s c a l e t o a n o t h e r , t h i s is a c c o m p l i s h e d by
*RE1,2
( 6 )
where is t h e e l e c t r o d e p o t e n t i a l r e l a t i v e t o t h e
second
r e f e r e n c e e l e c t r o d e (the d e s i r e d q u a n t i t y ) ,
is t h e e l e c t r o d e p o t e n t i a l r e l a t i v e t o t h e f i r s t
r e f e r e n c e e l e c t r o d e (the measured q u a n t i t y ) and
2
is t h e e l e c t r o d e p o t e n t i a l o f t h e f i r s t r e f e r e n c e
'
e l e c t r o d e r e l a t i v e t o t h e second r e f e r e n c e e l e c t r o d e .
2

40
CORROSION
CHEMISTRY
T a b l e I . E l e c t r o d e p o t e n t i a l s o f some common
r e f e r e n c e e l e c t r o d e s at 25C. (4)
Electrode Reaction/
Name o f R e f e r e n c e
Electrode
2Hg
+ 2C1~ = H g C l
0
+ 2e~ / C a l o m e l
Electrolyte
0.01 M KC1
0.10 M
1.0 M "
Satd.
11
0.1 M CuSO,
Cu = C u
+ 2e~ /
Copper-Copper
0.5 M
" *
Sulfate
Satd.
Ag + C l ~ = A g C l + e" 0.001 M KC1
Silver-Silver
0.01 M "
Chloride
2 +
Electrode
Potential
(V v s . SHE)
0.389
0.333
0.280
0.241
0.284
0.294
0.298
0.400
0.343
I l l u s t r a t i o n 2. C o n v e r s i o n o f R e f e r e n c e E l e c t r o d e
Scale.
I f t h e e l e c t r o d e p o t e n t i a l o f an i r o n e l e c t r o d e
is -0.528 V v s . s a t u r a t e d c a l o m e l r e f e r e n c e
e l e c t r o d e (SCE), what is i t s v a l u e r e l a t i v e t o
SHE?
Solution:
I n s e r t i n g t h e measured e l e c t r o d e p o t e n t i a l and
the e l e c t r o d e p o t e n t i a l o f t h e r e f e r e n c e e l e c t r o d e
from T a b l e I (
= 0.241 V v s . SHE) in
E q u a t i o n 6,
= -0.287 V v s . SHE.
0
Equilibrium
Electrode
Potentials.
The c o n d i t i o n f o r e q u i l i b r i u m f o r t h e e l e c t r o c h e m
i c a l r e a c t i o n g i v e n in E q u a t i o n 4 is
v
e eo
( 7 )
where t h e " c h e m i c a l " p o t e n t i a l o f t h e e l e c t r o n at

equilibrium, y
/ is r e l a t e d t o t h e e q u i l i b r i u m e l e c
t r o d e p o t e n t i a l o f t h e r e a c t i o n , , by
e
e o
(8)
where F is t h e F a r a d a y c o n s t a n t . The c h e m i c a l p o t e n t i a l
of a s p e c i e s , Y, is

2.
Electrochemical
D O N A H U E
41
Techniques
= + RT n a
(9)
I n s e r t i n g E q u a t i o n s 8 and 9 in 7 and r e a r r a n g i n g
= (1/^) + (RT/v F)n(n(a ) )
(10)
I t c a n be shown t h a t
=
(l/v F)Zv
e
(11)
yy
where is t h e s t a n d a r d e l e c t r o d e p o t e n t i a l o f t h e
r e a c t i o n . Tabulated values o f standard e l e c t r o d e poten
t i a l s r e l a t i v e t o SHE f o r many e l e c t r o c h e m i c a l r e a c t
i o n s o f i n t e r e s t in c o r r o s i o n a r e a v a i l a b l e () I n
s e r t i n g Equation 1
= + (RT/v F)n(II(a ) )
e
(12)
E q u a t i o n 12 may be used t o compute e q u i l i b r i u m

electrode potentials f o r electrochemical reactions.
I n o r d e r f o r such c a l c u l a t i o n s t o be c o n s i s t e n t w i t h
respect t o the s i g n of the p o t e n t i a l , the standard
e l e c t r o d e p o t e n t i a l s s h o u l d have s i g n s c o n s i s t e n t w i t h
t h o s e o f de Bethune (4) and t h e s t o i c h i o m e t r i c c o e f f i
c i e n t s s h o u l d be i n s e r t e d c o n s i s t e n t w i t h E q u a t i o n 4
as w r i t t e n .
A c t i v i t i e s and/or a c t i v i t y c o e f f i c i e n t s a r e n o t
a v a i l a b l e f o r i o n i c s p e c i e s in most c o r r o s i o n s o l u t i o n s .
T h e r e f o r e , as a p r a c t i c a l e x p e d i e n t , t h e c o n c e n t r a t i o n s
o f t h e s p e c i e s a r e used in p l a c e o f t h e r e s p e c t i v e
a c t i v i t i e s when computing e q u i l i b r i u m e l e c t r o d e p o t e n
tials .
Pourbaix
Diagrams.
I f an e l e c t r o c h e m i c a l r e a c t i o n is p e r t u r b e d from
the e q u i l i b r i u m s t a t e , t h e r e l a t i v e s t a b i l i t i e s o f t h e
s p e c i e s in t h e r e a c t i o n a r e changed. The m a n i f e s t a t i o n
o f t h e p e r t u r b a t i o n is t h e measured e l e c t r o d e p o t e n t i a l ,
w h i c h d i f f e r s from t h e e q u i l i b r i u m e l e c t r o d e p o t e n t i a l
f o r t h e r e a c t i o n . I f t h e measured e l e c t r o d e p o t e n t i a l
is p o s i t i v e w i t h r e s p e c t t o t h e e q u i l i b r i u m p o t e n t i a l ,
t h e r e a c t i o n g i v e n by E q u a t i o n 4 p r o c e e d s i r r e v e r s i b l y
from l e f t t o r i g h t , i . e . , t h e r e d u c e d form o f t h e
c h e m i c a l s p e c i e s is u n s t a b l e w h i l e t h e o x i d i z e d form
o f t h e s p e c i e s is s t a b l e . The c o n v e r s e is t r u e when t h e

42
CORROSION
CHEMISTRY
measured p o t e n t i a l is n e g a t i v e w i t h r e s p e c t t o t h e
equilibrium potential.
Water is an e l e c t r o c h e m i c a l l y a c t i v e c h e m i c a l
s p e c i e s . The e l e c t r o c h e m i c a l r e a c t i o n s in w h i c h w a t e r
is t h e p r i m a r y r e a c t a n t o r p r o d u c t a r e
2H 0 = 4 H
+ 0
+ 4e~
(13)
and
H
+ 20H~ = 2H 0 + 2e~
(14)
For s o l u t i o n s where t h e a c t i v i t y o f w a t e r is u n i t y and

t h e f u g a c i t i e s o f oxygen and hydrogen gases a r e u n i t y ,
the e q u i l i b r i u m e l e c t r o d e p o t e n t i a l s f o r t h e r e a c t i o n s
g i v e n by E q u a t i o n s 13 and 14 at 25C a r e r e s p e c t i v e l y
*O,H 0/0
2
=
2
"
and
* H / H 0 = -0-059PH
O /
(16)
where t h e s e e l e c t r o d e p o t e n t i a l s a r e V v s . SHE.
P o u r b a i x (1) has shown t h a t p l o t t i n g e l e c t r o d e
potentials of electrochemical reactions against solu
t i o n pH is u s e f u l in d e l i n e a t i n g r e g i o n s o f s t a b i l i t y
o f v a r i o u s c h e m i c a l s p e c i e s in and in c o n t a c t w i t h
aqueous s o l u t i o n s . These p l o t s a r e commonly c a l l e d
P o u r b a i x Diagrams. The u t i l i t y o f t h i s approach w i l l
become e v i d e n t in t h e subsequent p r e s e n t a t i o n .
The P o u r b a i x Diagram f o r t h e system, H 0-H -0 -H OH", is g i v e n in F i g u r e 2. The l i n e s "15" a n d
"16"
r e p r e s e n t p l o t s o f t h e d a t a f o r E q u a t i o n s 15 and 16,
r e s p e c t i v e l y . I n s p e c t i o n o f E q u a t i o n 13 and l i n e "15",
in c o n j u n c t i o n w i t h t h e p r e v i o u s d i s c u s s i o n o f s p e c i e s
s t a b i l i t y , i n d i c a t e s t h a t t h e s o l v e n t , w a t e r , is
s t a b l e ( w i t h r e s p e c t t o E q u a t i o n 13) at e l e c t r o d e
p o t e n t i a l s below t h i s l i n e w h i l e w a t e r is u n s t a b l e at
p o t e n t i a l s above t h i s l i n e . S i m i l a r l y , i n s p e c t i o n o f
E q u a t i o n 14 and l i n e "16" i n d i c a t e s t h a t w a t e r is
s t a b l e at e l e c t r o d e p o t e n t i a l s above l i n e "16" and
u n s t a b l e below t h e l i n e . F i g u r e 2 is a n a l o g o u s t o a
phase diagram; i t r e p r e s e n t s a form o f e l e c t r o c h e m i c a l
phase d i a g r a m . S i m i l a r t o a phase d i a g r a m , t h e r e g i o n
where a s p e c i e s is s t a b l e is i d e n t i f i e d w i t h t h e chem
i c a l symbol f o r t h e s p e c i e s .
The P o u r b a i x Diagram is p a r t i c u l a r l y u s e f u l in
d e t e r m i n i n g t h e s t a b l e s p e c i e s f o r m e t a l l i c systems in
+

2.
D O N A H U E
Electrochemical
43
Techniques
Figure 2. Pourbaix diagram for the system H 0-H -0 -H -OH~.

Activity of
water is unity; fugacities of hydrogen and oxygen are unity. Temperature is 25C.
2

44
CORROSION
CHEMISTRY
c o n t a c t w i t h aqueous s o l u t i o n s . Two g e n e r a l c l a s s e s o f
m e t a l s a r e found when F i g u r e 2 and t h e P o u r b a i x Diagram
f o r a m e t a l a r e superimposed. T h i s c l a s s i f i c a t i o n is
based on t h e r e l a t i o n s h i p between the m e t a l - m e t a l l i o n
e q u i l i b r i u m r e a c t i o n and the r e g i o n o f s t a b i l i t y o f
w a t e r . I n t h e f i r s t c a s e , the m e t a l - m e t a l l i o n e q u i l i brium p o t e n t i a l f a l l s w i t h i n the r e g i o n of s t a b i l i t y
o f w a t e r . I n t h e s e i n s t a n c e s , i t is p o s s i b l e t o measu r e t h e e q u i l i b r i u m e l e c t r o d e p o t e n t i a l o f the m e t a l m e t a l l i o n r e a c t i o n in aqueous s o l u t i o n s and t o d e v i s e
a means whereby the k i n e t i c p r o p e r t i e s o f t h i s r e a c t i o n
may be o b t a i n e d w i t h m i n i m a l k i n e t i c c o m p l e x i t y . The
second c l a s s o f m e t a l s has m e t a l - m e t a l l i o n e q u i l i b r i u m
e l e c t r o d e p o t e n t i a l s w h i c h f a l l below t h e r e g i o n o f
s t a b i l i t y o f w a t e r . S i n c e t h e s e m e t a l s form mixed
p o t e n t i a l systems w i t h t h e s o l v e n t (see b e l o w ) , t h e
equilibrium electrod
r e a c t i o n c a n n o t be
t h e k i n e t i c s o f the c o m p l e t e r e a c t i o n can be d e t e r m i n e d
o n l y w i t h g r e a t d i f f i c u l t y . Copper and i r o n a r e examples o f t h e s e two c l a s s e s o f m e t a l s and w i l l be d i s c u s s e d below.
F i g u r e 3 is the P o u r b a i x Diagram f o r copper and
some o f i t s i o n i c s p e c i e s and compounds in c o n t a c t
w i t h w a t e r at 25C. The e q u i l i b r i u m e l e c t r o d e p o t e n t i a l
f o r t h e c o p p e r - c u p r i c i o n r e a c t i o n is l o c a t e d w i t h i n
t h e r e g i o n o f w a t e r s t a b i l i t y (dashed l i n e s ) . T h e r e f o r e , t h e measurement o f t h e e q u i l i b r i u m p o t e n t i a l is
p o s s i b l e , and t h e k i n e t i c s o f t h e c o p p e r - c u p r i c i o n
system can be s t u d i e d w i t h o u t i n t e r f e r e n c e from r e a c t i o n s i n v o l v i n g d e c o m p o s i t i o n o f the s o l v e n t . W i t h
t h e e x c e p t i o n o f E q u a t i o n 21, w h i c h is a c h e m i c a l r e a c t i o n i n v o l v i n g the h y d r o l y s i s o f c u p r i c i o n ( r e a c t i o n s w h i c h a r e p u r e l y c h e m i c a l , s i n c e t h e y b e a r no
r e l a t i o n t o e l e c t r o c h e m i c a l r e a c t i o n s , p e r s e , appear
as v e r t i c a l l i n e s on P o u r b a i x D i a g r a m s ) , a l l o f t h e
r e a c t i o n s c o n s i d e r e d in F i g u r e 3 a r e e l e c t r o c h e m i c a l
and may be s t u d i e d u s i n g t h e t e c h n i q u e s o u t l i n e d in
t h i s c h a p t e r . I f the measured e l e c t r o d e p o t e n t i a l ( w i t h
r e s p e c t t o SHE) and t h e s o l u t i o n pH a r e known, F i g u r e 3
may be used t o d e t e r m i n e the s t a b l e form o f copper o r
i t s compounds w h i c h can be e x p e c t e d under t h o s e c o n ditions .
F i g u r e 4 is the P o u r b a i x Diagram f o r i r o n and
some o f i t s i o n i c s p e c i e s and compounds in c o n t a c t
w i t h w a t e r at 25C. The e q u i l i b r i u m p o t e n t i a l o f t h e
i r o n - f e r r o u s i o n r e a c t i o n f a l l s o u t s i d e the r e g i o n of
s t a b i l i t y o f w a t e r (dashed l i n e s ) . T h e r e f o r e , any attempt t o measure t h e e q u i l i b r i u m p o t e n t i a l w i l l f a i l
s i n c e t h e s o l v e n t w i l l undergo e l e c t r o c h e m i c a l r e d u c -

2.
D O N A H U E
Electrochemical
45
Techniques
Figure 3. Pourbaix diagram for the system Cu-Cu -Cu 0-H 0.

Activity of
cupric ion is assumed to be 0.01. The dashed lines denote the stability range of
water. Temperature is 25C. The reactions considered:
2+
Cu 0
Cu 0
2Cu
Cu *
2
+
+
+
+
Cu =
2H =
H0 =
H0 =
H0 =
+
Cu + 2e
2Cu + H 0 + 2e~
2CuO + 2H + 2e
Cu 0 + 2H + 2e~
CuO + 2H+
2+
2+

(17)
(18)
(19)
(20)
(21)
CHEMISTRY
CORROSION
14
pH
Figure 4. Pourbax diagram for the system Fe-Fe -Fe -Fe O -Fe 0 .
Activities of ferrous and ferric ions are JO" . Temperature is 25C. The reactions considered;
2+
3+
l4
Pe
3Fe + 4H 0
3Fe + 4H O
2Pe + 3H O
Pe
2P* + 3H O
2Fe O + H 0
2
2+
2+
2+
=
=
=
=
=
=
=
Pe r2e
Fe O + 8 + 8e~
Fe O + 8H + 2e~
Fe O + 6H + 2e~
P + e
Fe O + GIF
3Fe 0
+ 2H+ + 2e~
2+J

(22)
(23)
(24)
(25)
(26)
(27)
(28)
2.
D O N A H U E
Electrochemical
Techniques
47
t i o n w h i l e t h e i r o n w i l l undergo e l e c t r o c h e m i c a l o x i d a
t i o n . T h i s t y p e o f p r o c e s s is a form o f c o r r o s i o n and
is t h e b a s i s f o r an e l e c t r o c h e m i c a l model o f c o r r o s i o n
c a l l e d t h e t h e o r y o f mixed p o t e n t i a l s (to be d i s c u s s e d
below).
I n t h e p o t e n t i a l - p H r e g i o n where i r o n m e t a l is t h e
s t a b l e s p e c i e s , c o r r o s i o n - d e f i n e d as d i s s o l u t i o n o r
o x i d a t i o n - cannot occur s i n c e these r e a c t i o n s a r e n o t
f a v o r e d t h e r m o d y n a m i c a l l y . P o u r b a i x (1) has d e s i g n a t e d
t h e s e r e g i o n s a s "immune" t o c o r r o s i o n . However, in
t h e b r o a d e r sense o f c o r r o s i o n (see d e f i n i t i o n o f c o r
r o s i o n at t h e b e g i n n i n g o f t h i s c h a p t e r ) t h i s r e g i o n
may be q u i t e c o n d u c i v e t o i r o n d e t e r i o r a t i o n . F o r e x
ample, in t h i s r e g i o n hydrogen gas is s t a b l e (see F i g
u r e 2 ) . Some i r o n a l l o y s a r e s u s c e p t i b l e t o f r a c t u r e
in t h e p r e s e n c e o f hydrogen (_5) . T h e r e f o r e , i tisn o t
sufficient for a structur
in o r d e r f o r i t t o
When a c h e m i c a l l y s t a b l e o x i d e (or s a l t ) f i l m is
p r e s e n t on t h e s u r f a c e o f a m e t a l (see t h e i r o n o x i d e
s t a b l e r e g i o n s o f F i g u r e 4 ) , t h a t m e t a l may be f r e e
o f subsequent c o r r o s i o n . The c o n d i t i o n s f o r t h i s form
of c o r r o s i o n m i t i g a t i o n a r e that the underlying f i l m
is a d h e r e n t , c o h e r e n t and p o r e - f r e e . I n e s s e n c e , t h e s e
c o n d i t i o n s m e r e l y s t i p u l a t e t h a t t h e f i l m must be an
e f f e c t i v e b a r r i e r between t h e m e t a l and t h e e n v i r o n
ment. T h i s c o n d i t i o n is c a l l e d p a s s i v i t y and is c h a r
a c t e r i z e d by measured e l e c t r o d e p o t e n t i a l s in t h e r e
g i o n s where t h e f i l m is s t a b l e . I r o n and i t s a l l o y s
have been shown t o e x h i b i t p a s s i v e b e h a v i o r (6) .
F i g u r e 5 is a s i m p l i f i e d r e p r e s e n t a t i o n o f t h e
P o u r b a i x Diagram f o r i r o n . I t d e l i n e a t e s t h e r e g i o n s
where immunity, c o r r o s i o n and p a s s i v i t y c a n be e x p e c t
ed. S i m i l a r diagrams (as w e l l a s t h e more c h e m i c a l l y o r i e n t e d diagrams) a r e a v a i l a b l e in t h e monograph by
P o u r b a i x (1).
I l l u s t r a t i o n 3. Use o f P o u r b a i x Diagrams.
I d e n t i f y t h e s t a b l e s p e c i e s and whether c o r r o s i o n
is p o s s i b l e in t h e f o l l o w i n g s i t u a t i o n s :
a) copper m e t a l at +0.150 V v s . SCE in an aqueous
s o l u t i o n w i t h a pH o f 2.5 and a c u p r i c i o n
a c t i v i t y o f 0.01 at 25C.
b) i r o n m e t a l at -0.750 V v s . SCE in an aqueous
s o l u t i o n w i t h a pH o f 5.0 and a f e r r o u s i o n
6
a c t i v i t y o f 1 0 ~ at 25C.
Solutions :
a) t h e e l e c t r o d e p o t e n t i a l ( v s . SHE) is computed
u s i n g E q u a t i o n 6 and T a b l e I , i . e . , = 0.391 V
American Chemical
Society Library
1155 16th St. N. W.

Washington,
D. Brubaker,
C. 20036
In Corrosion Chemistry;
G., et al.;
48
CORROSION
v s . SHE.
CHEMISTRY
R e f e r r i n g t o F i g u r e s 2 and 3
the
2+
+
s t a b l e s p e c i e s a r e Cu
, H and H 0.
Corrosion
is p o s s i b l e under t h e s e c o n d i t i o n s ,
b) the e l e c t r o d e p o t e n t i a l (vs. SHE) is computed
u s i n g E q u a t i o n 6 and T a b l e I , i . e . , = -0.509
V v s . SHE. R e f e r r i n g t o F i g u r e s 2 and 4, the
s t a b l e s p e c i e s a r e f e r r o u s i o n s and H^.
Corr o s i o n is p o s s i b l e under t h e s e c o n d i t i o n s .
Electrochemical Kinetics
f
P r o p e r t i e s of E l e c t r o d e
Reactions.
E l e c t r o c h e m i c a l (electrode) r e a c t i o n s are i n h e r
e n t l y h e t e r o g e n e o u s The e l e c t r o n t r a n s f e r r e a c t i o n
o c c u r s at a m e t a l (o
substrate)-solutio
f o l l o w i n g the e l e c t r o n t r a n s f e r r e a c t i o n , t r a n s p o r t o f
c h e m i c a l s p e c i e s between the b u l k o f t h e s o l u t i o n and
the i n t e r f a c e a l s o t a k e s p l a c e . F i g u r e 6 is a r e p r e
s e n t a t i o n of these processes which c o n s t i t u t e the t o
t a l i t y o f the e l e c t r o c h e m i c a l r e a c t i o n .
The t h r e e s t e p s a s s o c i a t e d w i t h e l e c t r o c h e m i c a l
r e a c t i o n s , i . e . , t r a n s p o r t o f r e a c t a n t ( s ) t o the i n t e r
f a c e , the e l e c t r o n t r a n s f e r ( s u r f a c e ) r e a c t i o n and
t r a n s p o r t o f p r o d u c t ( s ) from the i n t e r f a c e , a r e sequen
t i a l . T h e r e f o r e , the o v e r a l l r a t e o f r e a c t i o n is c o n
t r o l l e d by t h e s l o w e s t o f the t h r e e s t e p s . When t h e
t r a n s p o r t p r o c e s s e s a r e c a p a b l e o f o p e r a t i n g at h i g h
r a t e s r e l a t i v e t o the e l e c t r o n t r a n s f e r r e a c t i o n , the
r a t e o f the o v e r a l l r e a c t i o n can be d e s c r i b e d by equa
t i o n s o f e l e c t r o d e k i n e t i c s . These t y p e s o f e l e c t r o d e
r e a c t i o n s a r e s a i d t o be "under a c t i v a t i o n c o n t r o l " .
On the o t h e r hand, when the e l e c t r o d e r e a c t i o n is
c a p a b l e o f o p e r a t i n g at h i g h r a t e s r e l a t i v e t o the
t r a n s p o r t p r o c e s s ( e s ) , the r a t e o f the o v e r a l l r e a c t i o n
can be d e s c r i b e d by e q u a t i o n s o f c o n v e c t i v e mass t r a n s
p o r t . These t y p e s o f e l e c t r o d e r e a c t i o n s a r e s a i d t o
be "under t r a n s p o r t c o n t r o l " . I n the d i s c u s s i o n t o
f o l l o w , the e q u a t i o n s o f e l e c t r o d e k i n e t i c s and c o n v e c t
i v e mass t r a n s p o r t w i l l be p r e s e n t e d w i t h the c o n d i
t i o n s under w h i c h the r e s p e c t i v e e q u a t i o n s a p p l y .
Readers w i s h i n g a more d e t a i l e d p r e s e n t a t i o n t h a n is
p o s s i b l e h e r e s h o u l d r e f e r t o t h e monograph by V e t t e r
(7) .
The r a t e o f an e l e c t r o c h e m i c a l r e a c t i o n is u s u a l l y
measured by a c u r r e n t , I , f l o w i n g in an e x t e r n a l e l e c
t r i c a l c i r c u i t (see b e l o w ) . T h i s c u r r e n t is r e l a t e d t o
the f l u x o f a r e a c t i n g s p e c i e s , N_, and the f l u x o f a

D O N A H U E
Figure 6.
Electrochemical
Techniques
Representation of transport and kinetic processes in electrode reactions

50
CORROSION
CHEMISTRY
p r o d u c t s p e c i e s , N , and t h e r a t e o f t h e s u r f a c e r e
a c t i o n (based on
the reacting species), r
by
R
Jf
I/nFA = j = /
= Tj
(29)
where is t h e number o f e l e c t r o n s t r a n s f e r r e d in t h e
in t h e e l e c t r o c h e m i c a l r e a c t i o n , A is t h e s u r f a c e a r e a
o f t h e m e t a l s u b s t r a t e in c o n t a c t w i t h t h e s o l u t i o n
and V j and v a r e t h e s t o i c h i o m e t r i c c o e f f i c i e n t s o f
the
r e a c t a n t and p r o d u c t s p e c i e s , r e s p e c t i v e l y .
The s i g n o f t h e c u r r e n t is dependent on t h e sense
o f t h e e l e c t r o c h e m i c a l r e a c t i o n . F o r example, when
E q u a t i o n 4 o p e r a t e s from l e f t t o r i g h t , i . e . ,
R
Red
-> Ox + n e "
(4a)
an e l e c t r o c h e m i c a l o x i d a t i o
i c a l o x i d a t i o n s are o f t e n c a l l e d anodic r e a c t i o n s . I n
t h e c o n v e n t i o n used in t h i s c h a p t e r , a n o d i c r e a c t i o n s
a r e a s s o c i a t e d w i t h p o s i t i v e c u r r e n t s . When t h e d i
r e c t i o n o f t h e r e a c t i o n is r e v e r s e d , i . e . ,
Ox + n e "
Red
(4b)
an e l e c t r o c h e m i c a l r e d u c t i o n ( c a t h o d i c r e a c t i o n )
occurs. Cathodic r e a c t i o n s are associated with negative
c u r r e n t s . The s i g n s o f t h e r a t e and f l u x terms in
E q u a t i o n 29 s h o u l d be a d j u s t e d t o accomodate t h i s s i g n
convention.
The r a t e ( c u r r e n t ) o f an e l e c t r o c h e m i c a l r e a c t i o n
is d e s c r i b e d by t h e sum o f t h e r a t e s ( c u r r e n t s ) o f t h e
a n o d i c and c a t h o d i c r e a c t i o n s w h i c h c o n s t i t u t e t h e
e l e c t r o d e r e a c t i o n . The a n o d i c and c a t h o d i c c u r r e n t s ,
representing "parts" of the o v e r a l l current (rate), are
called p a r t i a l currents.
Activation Controlled Electrode
Reactions.
A t e q u i l i b r i u m , t h e r a t e s o f t h e a n o d i c and c a t h
o d i c p a r t i a l r e a c t i o n s a r e e q u a l , i . e . , t h e r e is no
n e t change o f t h e i n v e n t o r y o f Red and Ox. When t h e
system is p e r t u r b e d such t h a t t h e e l e c t r o d e p o t e n t i a l
is p o s i t i v e w i t h r e s p e c t t o t h e e q u i l i b r i u m p o t e n t i a l ,
t h e r a t e o f t h e a n o d i c p a r t i a l r e a c t i o n is g r e a t e r
t h a n t h a t o f t h e c a t h o d i c p a r t i a l r e a c t i o n . The e l e c
trode r e a c t i o n e x h i b i t s a n e t anodic (oxidation) cur
rent. Likewise, f o r perturbations negative t o the
equilibrium p o t e n t i a l , the electrode reaction e x h i b i t s

2.
Electrochemical
D O N A H U E
Techniques
51
a net cathodic (reduction) current.

The e q u a t i o n w h i c h has been found t o d e s c r i b e t h e
current-electrode p o t e n t i a l behavior of a c t i v a t i o n
c o n t r o l l e d r e a c t i o n s is
I/A = i = i [ e x p ( n / 6
)-exp(-n/6 )]
(30)
where i is t h e n e t c u r r e n t d e n s i t y ( I / A ) , i is t h e
exchange c u r r e n t d e n s i t y , is t h e o v e r p o t e n t i a l and
$ and 3 a r e s o - c a l l e d T a f e l c o n s t a n t s ( s l o p e s ) .
The exchange c u r r e n t d e n s i t y is a measure o f t h e
i n t r i n s i c r e a c t i v i t y of the electrode r e a c t i o n , i . e . ,
t h e r a t e s o f t h e a n o d i c and c a t h o d i c p a r t i a l r e a c t i o n s
at t h e e q u i l i b r i u m p o t e n t i a l . The e m p i r i c a l e q u a t i o n
w h i c h o f t e n d e s c r i b e s t h e exchange c u r r e n t d e n s i t y is
a
= nFk [Red
where k is a s p e c i f i c r a t e c o n s t a n t , [Red] and [Ox]

a r e t h e c o n c e n t r a t i o n s o f t h e o x i d i z e d and r e d u c e d
forms o f t h e c h e m i c a l s p e c i e s , [Cat] is t h e c o n c e n t r a
t i o n o f a c a t a l y t i c s p e c i e s and , and a r e r e a c t
ion orders.
The o v e r p o t e n t i a l is d e f i n e d by
= -
(32)
where ^ is t h e p e r t u r b e d e l e c t r o d e p o t e n t i a l a s s o c i
ated
with a net current density, i . Overpotentials
f o r anodic r e a c t i o n s a r e p o s i t i v e w h i l e those f o r
cathodic reactions are negative.
A t l a r g e a n o d i c o v e r p o t e n t i a l s , E q u a t i o n 30
becomes
i = i exp[n/e ]
(33)
= B n(i/i )
(34)
or
a
where is t h e a n o d i c T a f e l c o n s t a n t o r s l o p e (see
a b o v e ) . E q u a t i o n 34 i n d i c a t e s t h a t - i d a t a f o r an
e l e c t r o d e r e a c t i o n are l i n e a r over a s p e c i f i e d range.
T h i s l i n e a r r e g i o n p r o v i d e s a c c e s s t o two i m p o r t a n t
e m p i r i c a l p a r a m e t e r s in E q u a t i o n 30, v i z . , t h e a n o d i c
T a f e l s l o p e and t h e exchange c u r r e n t d e n s i t y . The form
e r is t h e s l o p e o f t h e l i n e in t h i s l i n e a r r e g i o n . The
exchange c u r r e n t d e n s i t y is o b t a i n e d by e x t r a p o l a t i n g

52
CORROSION
CHEMISTRY
the l i n e f o r t h e l i n e a r r e g i o n d a t a t o t h e e q u i l i b r i u m
p o t e n t i a l , i . e . , =0. I n s p e c t i o n o f E q u a t i o n 34 shows
t h a t t h e c u r r e n t d e n s i t y o b t a i n e d by t h i s e x t r a p o l a t i o n
is n u m e r i c a l l y e q u a l t o t h e exchange c u r r e n t d e n s i t y .
At l a r g e (negative) c a t h o d i c o v e r p o t e n t i a l s ,
E q u a t i o n 30 becomes
i = -i exp[-n/B ]
(35)
= -B n(-i/i )
(36)
or
c
where 3 is t h e c a t h o d i c T a f e l c o n s t a n t o r s l o p e . The
u t i l i t y o f E q u a t i o n 36 f o r the a n a l y s i s o f e m p i r i c a l
k i n e t i c p a r a m e t e r s f o r c a t h o d i c p a r t i a l r e a c t i o n s is
identical to that fo
reactions.
When e l e c t r o c h e m i c a l r a t e d a t a , i . e . , e l e c t r o d e
p o t e n t i a l - c u r r e n t d e n s i t y d a t a , a r e p l o t t e d , i t is
o f t e n done on s e m i - l o g a r i t h m i c p a p e r . S i n c e t h e l o g
a r i t h m i c s c a l e o f t h i s paper is u s u a l l y "base 10",
t h e T a f e l s l o p e s w h i c h a r e measured a r e r e l a t e d t o
t h e T a f e l c o n s t a n t s in E q u a t i o n 30 by
c
= b/2.30
(37)
where b is t h e s l o p e measured on "base 10" p a p e r .

I l l u s t r a t i o n 4. A n a l y s i s o f E l e c t r o c h e m i c a l Rate
Data f o r A c t i v a t i o n C o n t r o l l e d R e a c t i o n s .
E s t i m a t e t h e exchange c u r r e n t d e n s i t y and T a f e l
s l o p e s f o r an e l e c t r o d e r e a c t i o n from t h e d a t a
g i v e n below.
i
i
i
mV v s .
mV v s .
mV v s .
SCE
2
2
2
SCE
SCE
mA/cm
mA/cm
mA/cm
280
150
- 2.6
100
210
0.96
270
57
0.42
205
140
- 3.1
260
32
200
0.00
- 3.9
130
250
18
- 4.6
110
195
-0.35
245
13
190
-0.64
110
- 5.6
240
9.5
- 6.8
100
185
-0.90
235
7.2
80
-10
180
-1.15
230
5.1
175
-1.37
60
-15
225
3.8
-21
40
170
-1.60
220
20
-32
2.5
165
-1.80
215
1.76
160
-2.10
-47
0
155
-2.30

2.
DONAHUE
Electrochemical
Techniques
53
Solution:
The d a t a a r e p l o t t e d in F i g u r e 7. The a n o d i c and
c a t h o d i c T a f e l s l o p e s ("base 10") a r e 40 and 120
mV, r e s p e c t i v e l y , and t h e exchange c u r r e n t d e n s i t y
is 1.0 mA/cm . T h e r e f o r e , t h e c u r r e n t d e n s i t y electrode p o t e n t i a l behavior o f t h i s a c t i v a t i o n
c o n t r o l l e d e l e c t r o d e r e a c t i o n is d e s c r i b e d by
i = 1.0[exp(n/17.4)-exp(-n/52.2)]
2
where t h e c u r r e n t d e n s i t y is in mA/cm
o v e r p o t e n t i a l is in mV.
Transport
Controlled Electrode
and t h e
Reactions.
As n o t e d above
from t h e s u r f a c e is
r e a c t i o n . The c o n v e c t i v e mass t r a n s p o r t e q u a t i o n s
w h i c h d e s c r i b e t h i s m a t e r i a l f l u x ( i n terms o f c u r r e n t
d e n s i t y and c o n s i s t e n t w i t h t h e s i g n c o n v e n t i o n p r o posed in t h i s c h a p t e r ) a r e
i =
(n/|v
R e d
|)Fk ([Red] -[Red] )

c
(38)
and
i = -(n/|v |)Fk ([0x] -[0x] )
0 x
(39)
where k is the mass t r a n s f e r c o e f f i c i e n t and t h e subs c r i p t s b and s r e p r e s e n t t h e b u l k and i n t e r f a c i a l

c o n c e n t r a t i o n s , r e s p e c t i v e l y . To t h e e x t e n t t h a t t h e
b u l k and i n t e r f a c i a l c o n c e n t r a t i o n s a r e a p p r o x i m a t e l y
t h e same o r d e r o f m a g n i t u d e , t h e k i n e t i c s o f t h e
e l e c t r o d e r e a c t i o n a r e a d e q u a t e l y d e s c r i b e d by E q u a t i o n
30. However, when t h e s e c o n c e n t r a t i o n s d i f f e r by an
o r d e r o f magnitude o r more, t h e r a t e o f t h e e l e c t r o d e
r e a c t i o n is c o n t r o l l e d by t h e r a t e o f mass t r a n s p o r t .
F i g u r e 8 shows t h e e l e c t r o d e p o t e n t i a l - c u r r e n t
d e n s i t y b e h a v i o r o f a c a t h o d i c p a r t i a l p r o c e s s demons t r a t i n g a c t i v a t i o n c o n t r o l , t r a n s p o r t c o n t r o l and t h e
t r a n s i t i o n r e g i o n between them. The dashed l i n e r e p r e s e n t s t h e e x t e n s i o n o f t h e T a f e l l i n e , i . e . , Equat i o n 36. T h i s dashed l i n e p r e d i c t s c u r r e n t d e n s i t i e s
w h i c h exceed t h e r a t e o f mass t r a n s p o r t - an i m p o s s i b i l i t y . The v e r t i c a l ( e l e c t r o d e p o t e n t i a l i n d e p e n d e n t )
l i n e represents the l i m i t i n g current density for the
p r o c e s s . A l t h o u g h m a t h e m a t i c a l r e l a t i o n s h i p s have been
p r o p o s e d f o r t h e t r a n s i t i o n r e g i o n , t h e i r u t i l i t y is
m i n i m a l s i n c e t h e l i m i t i n g c a s e s o f a c t i v a t i o n and
Q

54
CORROSION C H E M I S T R Y
I
0.1
1.0
10
l_
100
2
CURRENT DENSITY (mA/cm )

Figure 7.
Plot of data for Figure 4

DONAHUE
Electrochemical
Techniques
Figure 8. Electrode potential-current density behavior of a cathodic partial

process showing regions of activation control, transport control, and the transition
between them

CORROSION
56
CHEMISTRY
transport c o n t r o l represent the properties of the vast

majority of electrode reactions.
Mass t r a n s p o r t c o n t r o l o f e l e c t r o d e r e a c t i o n s c a n
be caused by one o f two p h y s i c a l p r o c e s s e s . I n t h e
f i r s t case, the i n t e r f a c i a l concentration of the r e a c t ant d r o p s t o z e r o , i . e . , t h e e l e c t r o n t r a n s f e r r e a c t i o n
consumes t h e s p e c i e s as q u i c k l y as i t a r r i v e s at t h e
i n t e r f a c e . I n t h e second c a s e , t h e i n t e r f a c i a l c o n c e n
t r a t i o n o f t h e p r o d u c t r e a c h e s s a t u r a t i o n . When t h e s e
c o n d i t i o n s p r e v a i l , t h e r a t e o f mass t r a n s p o r t is at
i t s l i m i t i n g (maximum) v a l u e . L i m i t i n g c u r r e n t d e n s i
ties, i ^
and i , f o r a n o d i c and c a t h o d i c p a r t i a l r e
actions, respectively, are
a
la
( n /
la
le
l Redl
) F k
[ R e d ]
(40)
(n/|v
-(n/|v |)Fk [Ox]
0 x
(42)
(43)
Ic
The v a l u e o f t h e mass t r a n s f e r c o e f f i c i e n t depends

on t h e p h y s i c a l system, t h e t r a n s p o r t i n g s p e c i e s ,
p h y s i c o c h e m i c a l p r o p e r t i e s o f t h e f l u i d and t h e f l u i d
f l o w r a t e . Methods o f e s t i m a t i n g mass t r a n s f e r c o e f f
i c i e n t s a r e g i v e n e l s e w h e r e (8-10).
I l l u s t r a t i o n 5. E s t i m a t i o n o f L i m i t i n g C u r r e n t
Density.
Estimate the l i m i t i n g current density f o r the
-7
r e d u c t i o n o f oxygen ( c o n c e n t r a t i o n , [Ox], - 10
3
-5
2
mole/cm ; d i f f u s i v i t y , D, - 10
cm / s e c ) t o a
r o t a t i n g c y l i n d e r ( r o t a t i o n speed, , = 95 s e c "S
r a d i u s , r , = 1.27 cm) i f t h e k i n e m a t i c v i s c o s i t y ,
-3
2
v, o f t h e s o l u t i o n is a p p r o x i m a t e l y
10
cm / s e c .
Solution:
The mass t r a n s p o r t c o r r e l a t i o n f o r a r o t a t i n g
c y l i n d e r is (90
Sh = 0.0627 R e
Sc
where, in t h i s c a s e ,
Sh = Sherwood Number = k r/D
2
Re = Reynolds Number = wr /v
2 / 3
1 / 3

2.
DONAHUE
Electrochemical
57
Techniques
Sc = Schmidtr Number = v/D

2
2 / 3
1 / 3
= O.0627 (D/r) ( a i r / v )
(v/D)
-3
= 6.58X10
cm/sec.
The e l e c t r o c h e m i c a l r e a c t i o n f o r oxygen r e d u c t i o n
+
0 + 4H + 4e -* 2H 0
Then, t h e l i m i t i n g c u r r e n t d e n s i t y , i . e . , E q u a t i o n
42, is
he = - 4 F k [ O x ]
is
= (-4 e q u i v / m o l e ) ( 9 . 6 5 X 1 0
(6.58X10"
= -2.54X10"
cm/sec)(10~
A-sec/equiv)
7
mole/cm )
A/cm .
C r i t e r i a f o r Contro
I t is u s e f u l t o be a b l e t o a s c e r t a i n a p r i o r i
w h i c h t y p e o f c o n t r o l o p e r a t e s f o r an e l e c t r o d e r e a c t i o n . I n o r d e r t o d e m o n s t r a t e how t h i s may be
a c h i e v e d , c o n s i d e r a c a t h o d i c p a r t i a l r e a c t i o n . The
key element in a s c e r t a i n i n g c o n t r o l is t h e r a t i o o f
the h y p o t h e t i c a l a c t i v a t i o n c o n t r o l l e d c u r r e n t dens i t y , E q u a t i o n 35, t o t h e l i m i t i n g c u r r e n t d e n s i t y ,
e.g., E q u a t i o n 42. T h i s r a t i o is
i/i
= (|v |i /nFk [Ox] )exp(-n/B )

0 x
(44)
F o r e l e c t r o d e r e a c t i o n s where t h i s r a t i o is 0.3 o r
l e s s , a c t i v a t i o n c o n t r o l o p e r a t e s . When t h e r a t i o is
1.0 o r g r e a t e r , t h e e l e c t r o d e r e a c t i o n is under
transport control.
I n s p e c t i o n o f E q u a t i o n 44 u n d e r l i n e s t h e r e l a t i v e
i m p o r t a n c e o f v a r i o u s p a r a m e t e r s in t h e s t u d y o f
e l e c t r o d e r e a c t i o n s . I t is e v i d e n t t h a t t h e a n a l y s i s
of a c t i v a t i o n c o n t r o l l e d e l e c t r o c h e m i c a l data f o r
r e a c t i o n s w i t h l a r g e exchange c u r r e n t d e n s i t i e s is
r e s t r i c t e d t o a s m a l l range o f o v e r p o t e n t i a l u n l e s s
the mass t r a n s f e r c o e f f i c i e n t is l a r g e . The mass t r a n s f e r c o e f f i c i e n t is g e n e r a l l y l a r g e f o r e x p e r i m e n t a l
arrangements l i k e r o t a t i n g d i s k s , r o t a t i n g c y l i n d e r s
and o t h e r systems c a p a b l e o f a c h i e v i n g h i g h f l u i d
v e l o c i t y r a t e s (90 . On t h e o t h e r hand, i f one wants t o
s t u d y t h e r e g i o n o f mass t r a n s p o r t c o n t r o l , i t is
n e c e s s a r y t o o p e r a t e at l a r g e ( n e g a t i v e , in t h e c a s e
o f c a t h o d i c r e a c t i o n s ) o v e r p o t e n t i a l s and l o w concent r a t i o n s o f t h e r e a c t a n t s p e c i e s . However, t h i s

58
CORROSION
CHEMISTRY
approach is n o t w i t h o u t i t s d i f f i c u l t i e s {9), e.g.,

t h e appearance o f a second e l e c t r o d e r e a c t i o n may in
fluence the data.
Electrochemical Kinetics of Corrosion
Processes
Mixed P o t e n t i a l Model o f C o r r o s i o n .
M e t a l l i c c o r r o s i o n processes which a r e chemical
in n a t u r e (see above) c a n be w r i t t e n in t h e f o l l o w i n g
g e n e r a l form
M + 0x
e n v
- M
Z +
+ Red
(45)
e n v
where M r e p r e s e n t s t h
d i z e d form o f t h e m e t a l ( f o r c o n v e n i e n c e , i t is w r i t
t e n as a m e t a l l i c i o n ) , Ox
represents the species
in t h e aqueous s o l u t i o n
which r e a c t s w i t h the
m e t a l in t h e c o r r o s i o n r e a c t i o n and Red
is t h e
m o d i f i e d form o f t h a t s p e c i e s . I n s p e c t i o n o f E q u a t i o n
45 shows t h a t i t is composed o f two e l e c t r o c h e m i c a l
partial reactions, i . e . ,
n
M -> M
z +
+ ze
(46)
and
0^
+ ze" + R e d ^
env
env

(47)
The a n o d i c p a r t i a l p r o c e s s , E q u a t i o n 46, g e n e r a t e s t h e
e l e c t r o n s w h i c h a r e used in t h e c a t h o d i c p a r t i a l p r o
c e s s , E q u a t i o n 47. T h i s model o f c o r r o s i o n p r o c e s s e s
is based on t h e t h e o r y o f mixed p o t e n t i a l s (11) and is
shown s c h e m a t i c a l l y in F i g u r e 9. The o r i g i n a l t h e o r y
o f mixed p o t e n t i a l s was based on t h e " s u p e r p o s i t i o n "
of p o l a r i z a t i o n curves f o r the r e s p e c t i v e p a r t i a l pro
c e s s e s (11-13). However, s i n c e many mixed p o t e n t i a l
systems ( p a r t i c u l a r l y c o r r o s i o n p r o c e s s e s ) i n v o l v e
i n t e r a c t i o n s among t h e r e a c t a n t s , t h e p r e s e n t a t i o n
o f mixed p o t e n t i a l s g i v e n h e r e w i l l c o n s i d e r t h e more
r e c e n t approach c o n s i d e r i n g t h e s e i n t e r a c t i o n s ( 1 4 ) .
M e t a l s where c o r r o s i o n p r o c e s s e s t a k e p l a c e a r e
u s u a l l y i s o l a t e d , i . e . , n o t in c o n t a c t w i t h an e x t e r
n a l e l e c t r i c a l c i r c u i t . Charge c o n s e r v a t i o n is t h e
n e c e s s a r y c o n d i t i o n f o r a mixed p o t e n t i a l p r o c e s s t o
l e a d t o c o r r o s i o n on an i s o l a t e d m e t a l , i . e . ,
.i.(
) = 0
j j corr'
V M

(48)
2.
DONAHUE
Electrochemical
Techniques
59
where A. is t h e s u r f a c e a r e a where t h e " j t h " p a r t i a l

p r o c e s s ^ o p e r a t e s , .(
) is t h e c u r r e n t d e n s i t y o f
the " j t h " p a r t i a l
p r o c e s s at t h e e l e c t r o d e
p o t e n t i a l for the i s o l a t e d electrode, i . e . , corrosion
potential,
E q u a t i o n 48 r e p r e s e n t s an o p e r a t i o n a l
definition
of the corrosion p o t e n t i a l , i . e . ,
t h a t e l e c t r o d e p o t e n t i a l where t h e sum o f t h e p a r t i a l
c u r r e n t s in a c o r r o s i o n p r o c e s s is z e r o . T h i s d e f i n i
t i o n is s i m i l a r t o t h a t f o r an e q u i l i b r i u m p o t e n t i a l .
However, t h e e s s e n t i a l d i f f e r e n c e between e q u i l i b r i u m
and mixed p o t e n t i a l s is t h a t o f i n v e n t o r y o f t h e r e a c t a n t and p r o d u c t s p e c i e s - mixed p o t e n t i a l systems
n e c e s s a r i l y i n v o l v e changes in t h i s i n v e n t o r y .
For uniform c o r r o s i o n , i . e . , t h e e n t i r e s u r f a c e
is a c c e s s i b l e t o t h e m e t a l o x i d a t i o n r e a c t i o n and
the e n v i r o n m e n t a l r e a c t i o n ( s ) , E q u a t i o n 48 becomes
3
.j (c o r r ') =
r
E q u a t i o n 49 w i l l be used s u b s e q u e n t l y t o d e v e l o p e x
p r e s s i o n s f o r t h e c o r r o s i o n c u r r e n t d e n s i t y f o r spe
c i f i c examples o f c o r r o s i o n systems.
When a m e t a l e l e c t r o d e is made p a r t o f an e l e c
t r i c a l c i r c u i t (see b e l o w ) , t h e n e t c u r r e n t d e n s i t y ,
i . e . , i = I / A , at a p e r t u r b e d p o t e n t i a l , . , in u n i f o r m
c o r r o s i o n is
i = _. ( )
(50)
E q u a t i o n 50 w i l l be used s u b s e q u e n t l y t o d e v e l o p
e l e c t r o c h e m i c a l r a t e e q u a t i o n s f o r s p e c i f i c examples
o f c o r r o s i o n systems.
Two A c t i v a t i o n C o n t r o l l e d P a r t i a l
Processes.
When t h e r e a r e two p a r t i a l p r o c e s s in a mixed

p o t e n t i a l system and b o t h a r e under a c t i v a t i o n c o n t r o l ,
the most p r o b a b l e forms o f t h e c u r r e n t d e n s i t i e s o f
the a n o d i c and c a t h o d i c p a r t i a l p r o c e s s e s a r e E q u a t i o n s
33 and 35, r e s p e c t i v e l y . F o r an i s o l a t e d m e t a l , t h e
overpotential (since the corrosion p o t e n t i a l represents
the p e r t u r b e d e l e c t r o d e p o t e n t i a l in t h i s case) is
1 = y
corr
(51)
S u b s t i t u t i n g t h e a p p r o p r i a t e forms o f t h e r e s p e c t i v e
c u r r e n t d e n s i t i e s f o r t h e p a r t i a l p r o c e s s e s and t h i s
d e f i n i t i o n in E q u a t i o n 49, one o b t a i n s

60
oa
e x
P< *corr-*oa>/ aa>

(
^>c^<<W*corr>/*cc>
where t h e a d d i t i o n a l s u b s c r i p t s , a and c , denote t h e

p r o p e r t i e s o f t h e r e s p e c t i v e p a r t i a l p r o c e s s e s . The
exchange c u r r e n t d e n s i t i e s in E q u a t i o n 52 have mathe
m a t i c a l forms s i m i l a r t o E q u a t i o n 31. I f i n t e r a c t i o n s
among t h e r e a c t a n t s a r e p r e s e n t ( 1 4 ) , t h e i n t e r a c t i n g
s p e c i e s behave l i k e c a t a l y s t s .
The f i r s t term in E q u a t i o n 52 is p r o p o r t i o n a l t o
the r a t e o f m e t a l d i s s o l u t i o n at t h e c o r r o s i o n p o t e n
t i a l , i . e . , t h e c o r r o s i o n r a t e . T h e r e f o r e , a measure
o f t h e c o r r o s i o n r a t e is t h e c o r r o s i o n c u r r e n t d e n s i t y ,
i
, w h i c h is d e f i n e d f o r t h i s c a s e as
c
i c o r r = ioaexp((
) / 3 )
= i (( -
)/ )
oc
o c c o r r " ce
r
(53)
A m a t h e m a t i c a l r e l a t i o n s h i p s i m i l a r t o E q u a t i o n 31 c a n
u s u a l l y be o b t a i n e d e x p e r i m e n t a l l y f o r t h e c o r r o s i o n
current density.
F o r a c o r r o d i n g m e t a l w h i c h is c o n n e c t e d t o an
e l e c t r i c a l c i r c u i t ( i n order t o study i t s electrode
p o t e n t i a l - c u r r e n t d e n s i t y p r o p e r t i e s - see b e l o w ) ,
the o v e r p o t e n t i a l is
= .-

= (.-
corr'
)+(
V Y
- )
corr '
(54)
S u b s t i t u t i n g t h e a p p r o p r i a t e forms o f t h e r e s p e c t i v e
c u r r e n t d e n s i t i e s and t h i s d e f i n i t i o n in E q u a t i o n 50,
one o b t a i n s
i = ioa ((
3 )((.-
^
c o r r -
o a )' / aa
^ * c o r r " )a/a3 )
) / U > exp ( ( - > / * )
- e x p ( ( -
(55)
V V Y
o c
cc
Noting the d e f i n i t i o n o f c o r r o s i o n current

i . e . , E q u a t i o n 53, E q u a t i o n 55 becomes
1
* i - * c o r r
a a
cc
density,
- ^ P ^ c o r r - ^ / f W
( 5 6 )
F o r c o n v e n i e n c e , one may d e f i n e a parameter c a l l e d

p o l a r i z a t i o n , , as
= .-
i corr
Y

(57)
2.
DONAHUE
Electrochemical
61
Techniques
w h i c h is t h e m i x e d p o t e n t i a l a n a l o g
I n s e r t i n g E q u a t i o n 5 7 in 5 6 y i e l d s
1
- corr
I e x
( e / e
aa ,
e x
P -
e / 6
of
cc
overpotential.
) 1
( 5 8 )
S i n c e E q u a t i o n 5 8 is i d e n t i c a l in f o r m t o E q u a t i o n 3 0 ,
the a n a l y s i s of data for mixed p o t e n t i a l systems
is
t h e same a s t h a t f o r s i m p l e e l e c t r o d e
reactions.
In s t u d i e s of r e a c t i o n mechanisms of the p a r t i a l
p r o c e s s e s , t h e f o l l o w i n g f o r m o f E q u a t i o n 50
is
useful
(15)
= nF{k[Red]
[Ox]
exp(
( -)/B
a a
-k[Red]
W h e n d a t a a r e t a k e n at f i x e d p o t e n t i a l ( s )
in
the r e
spective linear region(s)
(the s o - c a l l e d T a f e l
region)
of electrode p o t e n t i a l - c u r r e n t density
experiments
(so-called p o l a r i z a t i o n experiments) with appropriate
v a r i a t i o n o f c o n c e n t r a t i o n o f one o r more of
the
species,
the r e a c t i o n order(s) of the species
may
be computed, e . g . ,
for cathodic
data,
8
inlOx]
o)
(60)
,[Red],T
With j u d i c i o u s c h o i c e of e x p e r i m e n t a l c o n d i t i o n s and
appropriate a n a l y s i s of the data, the parameters
in
E q u a t i o n 59 c a n b e o b t a i n e d w i t h r e l a t i v e e a s e .
Once
these parameters are s p e c i f i e d , the e l u c i d a t i o n of
the r e a c t i o n mechanism(s)
c a n be a t t e m p t e d .
However,
no d i s c u s s i o n o f r e a c t i o n m e c h a n i s m s o r t h e
methods
u s e d t o d e v e l o p them w i l l be g i v e n h e r e .
I l l u s t r a t i o n 6. A n a l y s i s o f A c t i v a t i o n C o n t r o l l e d
Mixed P o t e n t i a l Data.
T h e d a t a g i v e n in t h e a c c o m p a n y i n g t a b l e s
are
f o r i r o n in s u l f u r i c a c i d . D e t e r m i n e :
a) t h e c o r r o s i o n p o t e n t i a l s a n d t h e
corrosion
current d e n s i t i e s for the three
systems;
b) t h e s p e c i f i c r a t e c o n s t a n t a n d t h e r e a c t i o n
order for hydrogen ion for free
corrosion;
c) t h e s p e c i f i c r a t e c o n s t a n t s a n d t h e r e a c t i o n
orders for hydrogen ion for the p a r t i a l

CORROSION
CHEMISTRY
processes.
+
[H ]
M
0.055
0.100
0.250
System
A
Symbol
CURRENT DENSITY (A/cm )

System A
System
System C
2
1.51X10"
3.78X10"
6.88X10"
3 3.35X10"
8.65X10"
1.58X10""
3 5.89X10"
1.91X10"
3.59X10"
4
3.23X10" -1.56X10"
7.60X10"
mV v s . SHE
-300
-325
-350
-375
-400
4 -8.80X10"
4 -1.44X10"
-425
-1.52X10"
- 3.31X10"
-450
-3.06X10"
-500
-8.27X10"
-550
-600
-2.16X10"
-5.66X10"
-5.70X10"
3
-1.50X10" -3.76X10"
3
-3.94X10" -9.84X10"
2
-1.03X10" -2.57X10"
Solutions :
a) The d a t a a r e p l o t t e d in F i g u r e 10. E x t r a p o l a t
ion of the T a f e l region data to the r e s p e c t i v e
intersections yields:
System
corr
-406
corr
1.33X10 -4
1.79X10 -4
-390
C
-367
2.85X10*-4
where t h e c o r r o s i o n p o t e n t i a l s a r e mV v s . SHE
and t h e c o r r o s i o n c u r r e n t d e n s i t i e s a r e A/cm .
b) I n o r d e r t o d e t e r m i n e t h e r e a c t i o n o r d e r o f
hydrogen i o n f o r f r e e c o r r o s i o n , p l o t l o g i
v s . l o g (hydrogen i o n c o n c e n t r a t i o n )
,i.e.,
the l o w e s t l i n e in F i g u r e 11. The s l o p e o f t h e
l i n e , 0.5, is t h e r e a c t i o n o r d e r f o r hydrogen
i o n under t h e s e c o n d i t i o n s . To compute t h e
s p e c i f i c r a t e c o n s t a n t , one n o t e s t h a t
2
corr/
4
where n=2 and F=9.65X10 A - s e c / e g u i v and k
" c o n t a i n s " t h e terms a s s o c i a t e d w i t h "Red".

DONAHUE
Electrochemical
M z+
Figure 9.
Techniques
_
Red.
env
env

SOLUTION
METAL
Schematic of corrosion as a mixed potential process
-300
CO
>
-400
3
W
EH
U
W
Q
-500 h
U
W
W
-600
CURRENT DENSITY
Figure 10.
(A/cm )
Polarization diagram for data in Figure 6


2.
DONAHUE
Electrochemical
65
Techniques
Then,
System
A
2.94X10"
2.93X10"
2.95X10~
mean v a l u e = 2.94X10""
c) I n o r d e r t o d e t e r m i n e t h e r e a c t i o n o r d e r s f o r
hydrogen i o n f o r t h e p a r t i a l p r o c e s s e s , choose
^=-325 mV f o r t h e a n o d i c p a r t i a l p r o c e s s d a t a
and .=-500 mV f o r t h e c a t h o d i c p a r t i a l
process
d a t a . P l o t t h e l o g (^) v s . l o g [ H ] ,
i . e . , t h e upper p a i r o f l i n e s in F i g u r e 1 1 .
The s l o p e s o f t h e s e l i n e s a r e t h e r e s p e c t i v e
reaction orders i . e .
=-1.0
d
=+1.0
The s p e c i f i
(see de Bethune () f o r t h e s t a n d a r d e l e c t r o d e
p o t e n t i a l s and T a f e l s l o p e s a r e from F i g u r e 10)
+
k=i [ H ] / n F
a a
and
exp((-325-(-440))/17)
k=-i /nF[H ] exp ( ( 0 - (-500))/51)

The d a t a f o r t h e s e a n a l y s e s :
c
System
A/ni
â
1.58X10"
8.65X10"
3.35X10*"
A/Cnt
5.46X10"
11
8.27X10*"
4.30X10"
5.44X10"
11
5.27X10"
11
12
1.50X10"
4.29X10""
12
3.76X10"
4.30X10"
12
The mean v a l u e s o f t h e c o n s t a n t s a r e :
k=5.39X10"
a
l:L
12
and k=4 . 30X10"" .

c
Two P a r t i a l P r o c e s s e s - One Under T r a n s p o r t

Control.
M i x e d p o t e n t i a l systems w i t h t h e c a t h o d i c p a r t i a l
p r o c e s s under t r a n s p o r t c o n t r o l and t h e a n o d i c p a r t i a l
p r o c e s s under a c t i v a t i o n c o n t r o l is t y p i c a l o f many
c o r r o s i o n systems. F o r t h e c a t h o d i c p a r t i a l p r o c e s s t o
be under t r a n s p o r t c o n t r o l , E q u a t i o n 44 must be u n i t y
o r l a r g e r . T h i s o c c u r s when t h e a b s o l u t e v a l u e o f t h e
d i f f e r e n c e between t h e e q u i l i b r i u m e l e c t r o d e p o t e n t i a l
o f t h e c a t h o d i c p a r t i a l p r o c e s s and t h e c o r r o s i o n is
on t h e o r d e r o f one v o l t . T h i s c o n d i t i o n p r e v a i l s f o r
most m e t a l s o f i n t e r e s t in c o r r o s i o n s t u d i e s i f oxygen

66
is p r e s e n t in the s o l u t i o n and f o r many m e t a l s when

c o n t a m i n a n t s l i k e f e r r i c and c u p r i c i o n s a r e p r e s e n t .
The c o r r o s i o n c u r r e n t d e n s i t y f o r t h i s c l a s s o f
c o r r o s i o n sytems (assuming t h a t t h e l i m i t i n g c u r r e n t
d e n s i t y f o r the c a t h o d i c p a r t i a l p r o c e s s is g i v e n by
E q u a t i o n 42) is
i
corr
= i
((
)/3
oa ^
corr oa"
(n/|v |)Fk [Ox]
0 x
aa
(61)
E q u a t i o n 61 d e m o n s t r a t e s t h a t the c o r r o s i o n r a t e f o r
t h i s c l a s s o f systems is c o n t r o l l e d u n i q u e l y by the
by the r a t e o f mass t r a n s p o r t . Comparing E q u a t i o n 61
w i t h E q u a t i o n 53 r e v e a l s t h a t t h e c o r r o s i o n p o t e n t i a l
is d e f i n e d by the n a t u r e s o f t h e a n o d i c and c a t h o d i c
p a r t i a l processes f o
at hand, the c o r r o s i o
magnitude o f t h e mass t r a n s f e r c o e f f i c i e n t - a p r o p e r t y
o f the c o n v e c t i v e mass t r a n s p o r t c o n d i t i o n .
The e l e c t r o d e p o t e n t i a l - c u r r e n t d e n s i t y b e h a v i o r
o f t h i s t y p e o f c o r r o s i o n system is
i - icorr^Pte/'W-
1 1
( 6 2 )
E q u a t i o n 62 p r e d i c t s T a f e l b e h a v i o r o n l y f o r a n o d i c
( p o s i t i v e ) p o l a r i z a t i o n . C a t h o d i c p o l a r i z a t i o n is
p r e d i c t e d t o be p o t e n t i a l i n d e p e n d e n t at l a r g e n e g a t i v e
p o l a r i z a t i o n s . However, f o r most c o r r o s i o n s y s t e m s ,
t h i s r e g i o n o f p o t e n t i a l independence is s m a l l due
to the presence of other c a t h o d i c p a r t i a l processes,
e.g., s o l v e n t d e c o m p o s i t i o n t o form hydrogen gas.
While these other cathodic p a r t i a l processes u s u a l l y
do n o t p a r t i c i p a t e in the c o r r o s i o n system per s e ,
t h e y a r e m a n i f e s t e d in the e x p e r i m e n t a l d a t a and can
cause d i f f i c u l t y in a n a l y z i n g t h e d a t a . Methods o f
compensating f o r t h e s e e f f e c t s have been employed
w i t h s u c c e s s (16_, 17) .
I l l u s t r a t i o n 7. E v a l u a t i o n o f Mass T r a n s p o r t
C o n t r o l l e d Data.
The d a t a g i v e n below a r e f o r c a t h o d i c p o l a r i z a t i o n
o f i r o n in 0.01 M s u l f u r i c a c i d in t h e p r e s e n c e
o f 0.53 M f e r r i c i o n . E s t i m a t e the l i m i t i n g c u r
r e n t d e n s i t y and mass t r a n s f e r c o e f f i c i e n t f o r
the r e d u c t i o n o f f e r r i c i o n under t h e s e c o n d i t i o n s .

2.
DONAHUE
Electrochemical
Techniques
67
-
mV v s . SHE
360
380
400
450
500
550
600
650
700
mA/cm'
0
1.30
4.54
4.89
5.37
5.96
7.57
11.6
22.0
Solution:
The d a t a a r e p l o t t e d in F i g u r e 12. A l t h o u g h t h e r e
is no u n e q u i v o c a l l y p o t e n t i a l i n d e p e n d e n t r e g i o n ,
t h e d a t a between -400 and -550 mV a p p r o x i m a t e
t h a t b e h a v i o r . Th
d e n s i t y over t h i
t o be t h e b e s t e s t i m a t e o f t h e l i m i t i n g c u r r e n t
density.
The e l e c t r o d e r e a c t i o n f o r f e r r i c i o n r e d u c t i o n is
=(5.2X10" )/(9,65X10 )(5.3X10~

= 1.02X10" cm/sec
mole/cm )
M u l t i p l e P a r t i a l Process
C o r r o s i o n Systems.
A l t h o u g h most c o r r o s i o n systems c a n be d e s c r i b e d
by t h e l i m i t i n g models p r e s e n t e d above, t h e r e a r e in
s t a n c e s where c o n t r o l o f t h e c o r r o s i o n system is a
combination o f both types, v i z . , a c t i v a t i o n c o n t r o l l e d
a n o d i c p a r t i a l p r o c e s s w i t h two c a t h o d i c p a r t i a l p r o
c e s s e s - one under a c t i v a t i o n c o n t r o l and a n o t h e r
under t r a n s p o r t c o n t r o l . Examples a r e i r o n c o r r o s i o n
in a c i d s o l u t i o n w i t h i n o r g a n i c c o n t a m i n a n t s (16_, 18)
and oxygen (7) . The c o r r o s i o n c u r r e n t d e n s i t y in
such systems is
corr
corr ' cc
)Pk [Ox]
c
(63)
where [Ox], is t h e b u l k c o n c e n t r a t i o n o f t h e "contam-

68
-300
-500
-700
10
-3
0
10
-2
Z
CURRENT DENSITY (A/cm )

Figure 12.
Pohrization diagram for data in Figure 7

2.
DONAHUE
Electrochemical
Techniques
69
i n a n t " . I t is e v i d e n t from E q u a t i o n 63 t h a t such m u l t i p l e c o n t r o l is a f o r t u i t o u s c o m b i n a t i o n o f p r o p e r t i e s

o f t h e r e s p e c t i v e c a t h o d i c p a r t i a l p r o c e s s e s and, w h i l e
observed, probably represents a " s p e c i a l case" o f the
o t h e r types o f c o r r o s i o n systems.
Experimental
Techniques
A l t h o u g h t h e o t h e r a u t h o r s in t h i s monograph have
d e s c r i b e d t h e i r e x p e r i m e n t a l systems in d e t a i l , i t is
worthwhile t o o u t l i n e the e s s e n t i a l features o f the
experimental e l e c t r o c h e m i c a l techniques which a r e
used t o measure and e v a l u a t e t h e v a r i o u s p a r a m e t e r s
d i s c u s s e d in t h i s c h a p t e r .
E l e c t r o d e P o t e n t i a l Measurements
The methods o f m e a s u r i n g e l e c t r o d e p o t e n t i a l s in
t h e absence o f an e x t e r n a l l y a p p l i e d c u r r e n t have
been g i v e n above. I n g e n e r a l , t h e s e comments a r e
a p p l i c a b l e t o p o l a r i z a t i o n e x p e r i m e n t s , as w e l l . The
m a j o r d i f f e r e n c e between " e q u i l i b r i u m " and p o l a r i z a t i o n measurements is t h a t , in t h e l a t t e r c a s e , an
ohmic v o l t a g e drop is p r e s e n t between t h e t e s t and
r e f e r e n c e e l e c t r o d e s due t o t h e f l o w o f c u r r e n t
t h r o u g h t h e r e s i s t i v e e l e c t r o l y t e (between t h e t e s t
and a u x i l i a r y - see below- e l e c t r o d e s ) . I n o r d e r t o
m i n i m i z e t h i s e f f e c t ( i t i n t r o d u c e s an e r r o r in t h e
measurements w h i c h v i r t u a l l y p r e c l u d e s t h e c o r r e c t
a p p l i c a t i o n o f , f o r example, E q u a t i o n 5 8 ) , one uses
a L u g g i n c a p i l l a r y (shown s c h e m a t i c a l l y in F i g u r e 1 3 ) .
S i n c e no c u r r e n t f l o w s in t h e v o l t a g e m e a s u r i n g c i r c u i t
(between t h e t e s t and r e f e r e n c e e l e c t r o d e s ) , t h e pot e n t i a l o f t h e s o l u t i o n at t h e t i p o f t h e c a p i l l a r y
is e q u a l t o t h e s o l u t i o n p o t e n t i a l at t h e r e f e r e n c e
e l e c t r o d e . T h e r e f o r e , i f t h e c a p i l l a r y t i p is l o c a t e d
close to the t e s t electrode, the actual i n t e r f a c i a l
p o t e n t i a l d i f f e r e n c e c a n be measured. B a r n a r t t (19)
has g i v e n a detail, ed a n a l y s i s o f t h e e f f e c t s o f such
capillaries.
E l e c t r o c h e m i c a l P o l a r i z a t i o n Systems.
F i g u r e 13 is a s c h e m a t i c r e p r e s e n t a t i o n o f t h e
t h r e e e l e c t r o d e system n o r m a l l y used in e l e c t r o c h e m i c a l
p o l a r i z a t i o n s t u d i e s . T h i s system i n c l u d e s two s e p a r a t e
e l e c t r i c a l c i r c u i t s . One o f t h e s e , between t h e t e s t
and r e f e r e n c e e l e c t r o d e s , is a v o l t a g e m e a s u r i n g

70
Figure IS.
Schematic of electrochemical polarization system

2.
DONAHUE
Electrochemical
Techniques
71
c i r c u i t and has been d i s c u s s e d above. The o t h e r c i r c u i t

p a s s e s c u r r e n t between t h e t e s t e l e c t r o d e and an auxi l i a r y e l e c t r o d e ( A E ) . S i n c e t h e p r o d u c t ( s ) formed at
the a u x i l i a r y e l e c t r o d e a r e e l e c t r o c h e m i c a l l y a c t i v e
and c o u l d be t r a n s p o r t e d t o t h e t e s t e l e c t r o d e , t h e
t e s t and a u x i l i a r y e l e c t r o d e s a r e u s u a l l y m a i n t a i n e d
in s e p a r a t e compartments w i t h a porous f r i t t e d g l a s s
d i s k o r i o n exchange membrane used t o m a i n t a i n e l e c t r o l y t i c t r a n s p o r t between t h e compartments. N o r m a l l y ,
t h e a u x i l i a r y e l e c t r o d e is e l e c t r o c h e m i c a l l y i n e r t ,
e.g., p l a t i n u m , b u t , on o c c a s i o n , t h e a u x i l i a r y
e l e c t r o d e is t h e same m a t e r i a l as t h e t e s t e l e c t r o d e .
The c o n t a i n e r used f o r t h e s e s t u d i e s s h o u l d be i n e r t ,
e.g., g l a s s , t e f l o n , e t c . S i n c e t h e d e s i g n s f o r s u c h
c o n t a i n e r s a r e as d i v e r s e as t h e number o f r e s e a r c h e r s ,
no recommendations w i t h r e s p e c t t o d e s i g n w i l l be
given here.
Two methods a r
between t h e t e s t and a u x i l i a r y e l e c t r o d e s . These a r e
the c o n s t a n t c u r r e n t ( g a l v a n o s t a t i c ) and c o n s t a n t
e l e c t r o d e p o t e n t i a l ( p o t e n t i o s t a t i c ) methods. The
former u t i l i z e s a c o n s t a n t v o l t a g e s o u r c e w i t h a
v a r i a b l e r e s i s t a n c e and ammeter in s e r i e s between t h e
t e s t and a u x i l i a r y e l e c t r o d e s . T h i s t y p e o f a r r a n g e ment is s i m p l e and c a n be used f o r most e l e c t r o c h e m i c a l s t u d i e s . The p o t e n t i o s t a t i c method is more
complex, b u t is e s s e n t i a l f o r s t u d i e s where mass t r a n s p o r t e f f e c t s o r p a s s i v i t y phenomena a r e t o be s t u d i e d .
P o t e n t i o s t a t s ( a v a i l a b l e c o m m e r c i a l l y ) o p e r a t e by
comparing t h e a c t u a l p o t e n t i a l d i f f e r e n c e between t h e
t e s t and r e f e r e n c e e l e c t r o d e s w i t h a " d e s i r e d " p o t e n t i a l d i f f e r e n c e and by p a s s i n g a c u r r e n t between t h e
t e s t and a u x i l i a r y e l e c t r o d e s w h i c h makes t h e " d i f f e r ence" z e r o . L a r g e impedances, p a r t i c u l a r l y in t h e
v o l t a g e m e a s u r i n g c i r c u i t , s h o u l d be a v o i d e d in systems
using potentiostats.
As n o t e d above, p o t e n t i o s t a t s a r e p a r t i c u l a r l y
s u i t e d t o t h e s t u d y o f mass t r a n s p o r t p r o c e s s e s and
p a s s i v i t y phenomena. I n t h e c a s e o f t r a n s p o r t p r o cesses, the instantaneous f l u x (current density) of
t h e p r o c e s s c a n be measured e a s i l y in t h e r e g i o n o f
mass t r a n s p o r t c o n t r o l w h i l e , w i t h g a l v a n o s t a t i c
e x p e r i m e n t s , t h e e l e c t r o d e p o t e n t i a l at t h e l i m i t i n g
c u r r e n t d e n s i t y is u n s t a b l e and e i t h e r d r i f t s s l o w l y
o r o s c i l l a t e s . The u t i l i t y o f p o t e n t i o s t a t s in p a s s i v i t y s t u d i e s is d e m o n s t r a t e d in F i g u r e 14. The s o l i d
c u r v e r e p r e s e n t s t y p i c a l d a t a o b t a i n e d at p a s s i v a t i n g
m e t a l s u s i n g a p o t e n t i o s t a t w h i l e t h e dashed l i n e
r e p r e s e n t s t h e d a t a in t h e p a s s i v e r e g i o n w h i c h one
o b t a i n s u s i n g a g a l v a n o s t a t . I t is e v i d e n t t h a t i t

72
LOG CURRENT DENSITY

Figure 14. Comparison of potentiostatic (
) and galvanostatic (
) data in
the passive region for metals capable of passivating during anodic polarization

2.
DONAHUE
Electrochemical
73
Techniques
is o n l y w i t h a p o t e n t i o s t a t t h a t one c a n measure t h e
passive current density, i
, (which p r o v i d e s a b a s i s
f o r d e t e r m i n i n g whether
anodic p r o t e c t i o n o f a
s t r u c t u r e is a d v i s a b l e ) .
p
Symbols/Nomenclature
Symbol
A
a
b
Cat
e"
F
Significance
Surface area
Activity
T a f e l s l o p e (base "10"
C a t a l y s t in r e a c t i o n
Electron
Faraday c o n s t a n t
Thermodynami
lation
K i n e t i c / T r a n s p o r t calcu
4
G
H
I
i
k
k
c
n
M
Ox
R
Red
l a t i o n s (=9.65X10 )
Free Enthalpy
Enthalpy
Current
Current density
S p e c i f i c rate constant
Mass t r a n s f e r c o e f f i c i e n t
Units
2
cm
V
-
A-sec/equiv
cal/mole
cal/mole
A
A/cm
(variable)
cm/sec
2
Natural logarithm
Metal
Flux
mole/cm s e c
Number o f e l e c t r o n s in
equiv
reaction
O x i d i z e d form o f c h e m i c a l
species
Gas c o n s t a n t (=1.99)
cal/mole-K
Reduced form o f c h e m i c a l
species
Temperature
K
Number o f e l e c t r o n s in
metal o x i d a t i o n r e a c t i o n -D
mole/cm
Concentration
V
T a f e l s l o p e (base "e")
Reaction order of Cat
Polarization
V
V
Electrode potential
Overpotential
V
Chemical p o t e n t i a l
cal/mole
S t o i c h i o m e t r i c c o e f f i c i e n t mole
R e a c t i o n o r d e r o f Red
R e a c t i o n o r d e r o f Ox
-

74
Symbol
Significance
Units
Superscripts.
z+
Standard p r o p e r t y
I o n i c c h a r g e on m e t a l l i o n -
Subscripts.
a
b
c
corr
e
env
J
j
satn
Y
298
P r o p e r t y o f anode o r
anodic r e a c t i o n
Property o f bulk
solution
P r o p e r t y o f cathode o r
cathodic reaction
P r o p e r t y at f r e e c o r r o s i o n Property of e l e c t r o n
Propert
Propert
species
Property o f " j t h " par
t i a l process
Property o f product
species
L i m i t i n g (maximum) p r o p
erty
Equilibrium property
P r o p e r t y at s a t u r a t i o n
P r o p e r t y o f any c h e m i c a l
species
P r o p e r t y at 298K
Literature Cited
1. P o u r b a i x , M. " A t l a s o f
Electrochemical
Equilibria",
Pergamon, O x f o r d , 1966.
2. - "JANAF Thermochemical T a b l e s " , U. S. Department
o f Commerce, Washington, 1965.
3. L e w i s , G. ., Randall, M., Pitzer, K. and Brewer,
L. "Thermodynamics", 2nd Edition, pp. 669-686,
M c G r a w - H i l l , New Y o r k , 1961.
4. de Bethune, A. J., Licht, T. S. and Swendeman, .,
J. E l e c t r o c h e m . Soc., (1959), 106, 616.
5. L o u t h a n , M. R. " P r o c e s s
Industries
Corrosion",
pp. 126-134, NACE, Houston, 1975.
6. Uhlig, H. H. " C o r r o s i o n and C o r r o s i o n
Control",
2nd
Edition,
pp. 60-91, W i l e y , New Y o r k , 1971.
7. Vetter, K. J. " E l e c t r o c h e m i c a l
Kinetics",
Academic,
New Y o r k , 1967.
8. W e l t y , J. R., W i c k s , C. E. and W i l s o n , R. E. "Fun
d a m e n t a l s o f Momentum, Heat and Mass T r a n s f e r " ,
pp. 578-589, W i l e y , New Y o r k , 1969.

2.
DONAHUE
Electrochemical Techniques
9.
75
D o n a h u e , F. M . " F u n d a m e n t a l s o f
Electrochemical
Engineering",
Chapter
IX,
Engineering
Summer C o n
ferences,
University
of
Michigan,
A n n Arbor, 1 9 7 8 .
1 0 . D o n a h u e , F. M .
"Physicochemical
Processes
f o r Water
Quality
Control",
W. J. W e b e r ,
Editor,
pp. 467-468,
Wile-Interscience,
New York, 1 9 7 2 .
11. W a g n e r , C . a n d Traud, W . , Z .
Elektrochem.,
(1938),
44, 391.
12.
Stern,
M . and G e a r y , A .
L.,
J.
Electrochem.
Soc.,
(1957),
104, 56.
13.
Stern,
M.
J.
Electrochem.
Soc.,
(1957), 104, 645.
14. Donahue,
F.
M.,
J.
Electrochem.
Soc.,
(1972), 119,
72.
15. D o n a h u e , F. M . " F u n d a m e n t a l s o f
Electrochemical
Engineering",
Chapter
X,
Engineering
Summer C o n
ferences,
University
of
Michigan,
Ann
Arbor,
1978
16.
Makrides,
A.
C.,
J.
Electrochem.
Soc.,
107, 869.
1 7 . D o n a h u e , F. M . a n d N o b e , K . " S e c o n d
International
Congress on
Metallic
Corrosion",
pp. 916-924,
NACE, H o u s t o n , 1966.
18.
Gatos,
H.,
Corrosion,
(1956), 12, 322t.
19.
Barnartt,
S.,
J.
Electrochem.
Soc.,
(1961), 108,
102.
RECEIVED September 1, 1978.

3
High-Temperature Corrosion
J. B R U C E W A G N E R , JR.
Center for Solid State Science, Arizona State University, Tempe, A Z 85281
T h e p u r p o s e of t h i s review p a p e r is to s u r v e y the
princi
ples of h i g h t e m p e r a t u r e o x i d a t i o n o r h i g h t e m p e r a t u r e
corro
s i o n . A typical s i t u a t i o
w h i c h c a n act a s a n o x i d a n t
duct f o r m s a layer w h i c h s e p a r a t e s the r e a c t a n t s , the m e t a l and
the gas a t m o s p h e r e .
U n d e r special c o n d i t i o n s , the k i n e t i c s a r e
d i f f u s i o n c o n t r o l l e d , i.e., the r a t e of the reaction (the r a t e of
o x i d e t h i c k n e s s g r o w t h ) depends on the d i f f u s i o n of s p e c i e s ,
i o n s and e l e c t r o n s , t h r o u g h the layer ( s o m e t i m e s c a l l e d a tar
nish
layer).
Actually
when a m e t a l o r alloy is e x p o s e d to a cor
rosive g a s , the r e a c t i o n k i n e t i c s m a y be c o n t r o l l e d by one o r
m o r e of the f o l l o w i n g steps:
1.
T r a n s p o r t of r e a c t a n t g a s e s to the s u r f a c e .
2.
T r a n s p o r t of r e a c t a n t s ( o r p r o d u c t s ) t h r o u g h a b o u n d a r y
layer adjacent to the s u r f a c e .
3.
A s u r f a c e c o n t r o l l e d reaction ( p h a s e b o u n d a r y r e a c t i o n ) at
the g a s - m e t a l i n t e r f a c e .
4.
T r a n s p o r t of r e a c t a n t s t h r o u g h a corrosion p r o d u c t l a y e r
e i t h e r b y b u l k d i f f u s i o n o r by migration t h r o u g h cracks and
pores.
In the p r e s e n t p a p e r , a t t e n t i o n will be f o c u s e d on the f o u r t h s t e p
i n v o l v i n g b u l k d i f f u s i o n . T h i s is a
classical
electrochemical
s i t u a t i o n i n v o l v i n g a n anode (the m e t a l ) w h e r e o x i d a t i o n o c c u r s
and a cathode (the o x i d e at the o x i d e - g a s i n t e r f a c e ) w h e r e r e d u c
t i o n of o x y g e n occurs. T h e o x i d e layer a c t s as the s o l v e n t f o r
point defects w h i c h diffuse t h r o u g h i t as will be d i s c u s s e d b e l o w .
C o n s i d e r the d i a g r a m s h o w n in Figure 1. T h e o x i d e layer
t h i c k e n s w i t h t i m e and s o the r a t e of o x i d a t i o n ( g o v e r n e d by d i f
f u s i o n t h r o u g h the o x i d e l a y e r ) d e c r e a s e s w i t h t i m e , t . T h i s s p e c c i a l s i t u a t i o n y i e l d s the p a r a b o l i c r a t e l a w f i r s t r e p o r t e d by
T a m m a n (j_) and by P i l l i n g and B e d w o r t h (2).
T a m m a n ' s rate
e q u a t i o n was s t a t e d in t e r m s of t a r n i s h l a y e r t h i c k n e s s , ,
0-8412-0471-3/79/47-089-076$05.00/0

3.
WAGNER
High-Temperature
Corrosion
77
and is
whence
()
= 2k.pt
(2)
where k^ is the Tamman rate constant with dimensions of c m

sec. The Pilling-Bedworth rate equation was expressed in
terms of weight change per unit area, Am/A.
It is
i ^ )
= V
(3)
where k is the Pilling-Bedworth rate constant with dimensions

of gm /cm sec. Thes
is shown schematicall
O r i g i n a l l y it was thought that oxidation proceeded by the
m i g r a t i o n of oxygen molecules through the product layer to the
metal. A c l a s s i c experiment known as m a r k e r movement was
performed by P f e i l (3^) in 1929 which in principle can d i s t i n
guish whether the migrating species occurs f r o m the gas atmos
phere inward or f r o m the metal outward through the oxide. ( F i g . 3 )
P f e i l placed some inert oxide particles ( m a r k e r s ) on the metal
surface ( i r o n ) p r i o r to oxidation. A f t e r oxidation had proceeded
for some time, he examined the c r o s s sections of the samples
and determined the location of the inert oxide p a r t i c l e s , the
m a r k e r s . It was found on i r o n that the particles remained at the
metal-oxide interface indicating that the migrating species were
the i r o n atoms diffusing f r o m the metal-oxide interface to the
oxide-gas interface. If the m a r k e r s remained at the oxide-gas
interface,then the inference would be that oxygen would have
migrated inward towards the metal. These l i m i t i n g cases can
be visualized by imagining the moving atomic species as impart
ing momentum to the m a r k e r as they move past them. It
p
* T h e two rate constants are related by
where Z Q denotes the valence of the oxidant (oxygen in the

example), the equivalent volume of the oxide, and A Q the
atomic weight of the oxidant.

film thickness,
or weight
go in per unit
area, Am/A
time
>
Figure 1. Schematic of film thickness or gaininweight per unit area vs. time for
oxidation of a pure metal where diffusion is rate controlling. The kinetics are
denoted as parabolic oxidation kinetics.
time
Figure 2.
>
Schematic of parabolic oxidation kinetics replotted from data of Fig

ure 1

3.
WAGNER
High-Temperature
79
Corrosion
remained for C a r l Wagner (4) to p e r f o r m the c l a s s i c e x p e r i ment to distinguish the mobile species in a c o r r o s i o n e x p e r i ment. H i s experimental set-up is shown in Figure 4. The overa l l reaction he studied was
2Ag(s) + S ( 1 ) = A g S ( s ) .
2
His set-up provided an a r t i f i c i a l reaction product l a y e r of two

preweighed s i l v e r sulfide pellets separating the reactants,
liquid sulfur and the s i l v e r pellet which was also preweighed.
A f t e r one hour a l l the pellets were reweighed. The pellet adjacent to the liquid sulfur had gained 124 mg while the pellet adjacent to the s i l v e r had not changed weight but the s i l v e r pellet
had lost exactly one milliequivalent of weight ( 108 mg). Thus
for this system, s i l v e r migrates f r o m the s i l v e r pellet through
both s i l v e r sulfide pellet
the s i l v e r sulfide-sulfu
The mechanism of diffusion through the c o r r o s i o n product
was s t i l l to be decided. C. Wagner proposed (4) that the m i grating particles involved ions and electrons, the ions migrating v i a defects. These lattice defects may be m i s s i n g cations or
anions (vacancies ) or cations or anions located in i n t e r s t i t i a l
positions. The state of stoichiometry, i.e. , s t r i c t adherence to
Dalton's law is not usual in most inorganic compounds and the
attainment of this state occurs only at well-defined temperatures
and chemical potentials of the constituents. Krftger and Vink
(5_) developed a notation for point defects whereby a l l the ions of
usual charge on usual lattice sites are denoted without charges
while the defects, vacancies or i n t e r s t i t i a l s , exhibit a charge
relative to these ions on usual sites. Superior p r i m e s denote
negative charges and superior heavy dots denote positive
charges. Consider an oxide, MO, wherein both ions are normally divalent. The disorder in stoichiometric c r y s t a l s may be
classified in the following l i m i t i n g cases and an equilibrium
constant (a function of temperature only) relates the concentrations of each as follows:
1.
Schottky Disorder: Equal concentrations of cation vacancies and anion vacancies
K
2.
(4)
^ M^ 0^
F r e n k e l Disorder: Equal concentrations of cation vacan

cies and interstitial cations
K
3.
(5)
Anti-Schottky Disorder:
Equal concentrations of cation

METAL OXIDE
inert
BEFORE
OXIDATION
M A
AFTER
inert
markers
OXIDATION
Figure 3. Schematic location of inert markers before oxidation (on the surface of
the pure metal) and after oxidation (at the metal-metal oxide interface). From
this limiting case one may infer that the mobile species diffuses from the metalmetal oxide interface outward through the scale or tarnish layer. If the marker
were found at the oxide-gas interface, the inference would be that the mobile
species diffused from the oxide-gas interface to the metal-oxide interface.
S (liquid)
+ 2Ag -2e-=Ag S === S
R
2Ag+ 2e~
] Ag -108 mg
Figure 4. Schematic of the experimental setup used by C. Wagner (4) to determine the location of the reaction 2kg + S = Ag S and the migrating species (silver) through the artificially prepared tarnish layer of Ag S separating the reactants,
silver and liquid sulfur
2

3.
WAGNER
High-Temperature
81
Corrosion
and anion interstitials

A-S
4.
i ^
(*>
A n t i - F r e n k e l D i s o r d e r : E q u a l c o n c e n t r a t i o n s of a n i o n
vacancies and anion interstitials
K
5.
= t i ^
= [O';][O:']
(7)
Anti-Structural Disorder:
and anions on cation sites
K
Anti-Str.
Cations located on anion sites
0 ^ M ^
The above considerations apply to stoichiometry.

Fornons t o i c h i o m e t r i c c o m p o u n d s , the e x c e s s o r d e f i c i t of a component
m a y a l s o be e x p r e s s e d
equations.
In v i e w of the l i m i t a t i o n s of s p a c e , c o n s i d e r a f e w s e l e c t e d
examples.
T h e o x i d a t i o n o f c o b a l t is o n e o f t h e b e t t e r s t u d i e d
systems.
C o b a l t o u s o x i d e is a m e t a l d e f i c i t c o m p o u n d .
The
r a t i o o f C o t o is l e s s t h a n o n e . A t a g i v e n t e m p e r a t u r e t h e
e q u a t i o n f o r t h i s s i t u a t i o n m a y be w r i t t e n a s
o (g)
= o
+ v ^
+h*
(9)
w h e r e t h e n o t a t i o n o f K r 8 g e r a n d V i n k is a g a i n u s e d .
S u p e r i o r p r i m e s and heavy dots denote effective negative
and positive c h a r g e s , r e s p e c t i v e l y .
Ions o n n o r m a l l a t t i c e s i t e s
are designated with no effective charge while defects a r e d e s i g
nated w i t h e f f e c t i v e c h a r g e s r e l a t i v e to the n o r m a l i o n s .
Thus a
n i c k e l o u s i o n o n a n o r m a l s i t e in n i c k e l o x i d e is d e n o t e d a s N i - ^
a n d a n i c k e l i c i o n in N i O w o u l d b e d e n o t e d a s N i j ^ . T h e
" e x t r a " o x y g e n is a c c o m o d a t e d o n a n o r m a l l a t t i c e s i t e a n d a
cobalt i o n vacancy (with a single effective negative charge) plus
o n e c o m p e n s a t i n g e l e c t r o n h o l e is f o r m e d . A n a l t e r n a t i v e
d e s c r i p t i o n o f t h e e l e c t r o n h o l e is a c o b a l t i c i o n ( C o
or Co )
s i t u a t e d in a s u b l a t t i c e o f n o r m a l l y c o b a l t o u s i o n s . T h e e q u i l i
b r i u m c o n s t a n t f o r E q . ( 9 ) is w r i t t e n a s
+ + +
io
= [v ][h*]/
= exp(-AG^Q /RT)
p*
(10)
= e x p C f - ^ +TAS^)/RT]

(11)
82
w h e r e A G | O > | a n d A s | o denote the p a r t i a l m o l a r f r e e

e n e r g y , e n t h a l p y a n d e n t r o p y of d i s s o l u t i o n of o n e - h a l f m o l e
oxygen into cobaltous oxide.
In v i e w of the r e q u i r e m e n t of e l e c
t r i c a l n e u t r a l i t y in t h e o x i d e [ ]
"]
Consequently,
2
1 0
= C v ^
/ P
'
T h u s i f one s o l v e s e x p l i c i t l y f o r the c a t i o n v a c a n c y
o r the e l e c t r o n hole
concentration
concentration,
- ^ " - - S ^
Because D
ce [ V < ^ ] t h e n i f o n e m e a s u r e d t h e r a d i o t r a c e r d i f f u s i o n o f c o b a l t in C o O , t h e i s o t h e r m a l o x y g e n p r e s s u r e d e p e n dence should exhibit a one-quarter dependence.
T h i s is e x a c t l y
w h a t C a r t e r a n d R i c h a r d s o n (6_) d i d . T h e i r r e s u l t s a r e s h o w n
in F i g u r e 5. T h e e l e c t r o n i c c o n d u c t i v i t y , , is
Q
a=[h]u q
(14)
w h e r e the s y m b o l u, d e n o t e s the m o b i l i t y of a n e l e c t r o n h o l e
a n d is h e r e a s s u m e d n o t t o b e d e p e n d e n t o n c o m p o s i t i o n .
Be
c a u s e [ h ] cc p o f t h e n t h e i s o t h e r m a l e l e c t r o n i c c o n d u c t i v i t y
s h o u l d a l s o be d e p e n d e n t u p o n the o n e - q u a r t e r p o w e r of the
oxygen pressure.
T h i s behavior was r e p o r t e d by E r o r and
W a g n e r (7_) ( s e e F i g u r e 6 ) .
T h e d i f f u s i v i t y o f o x y g e n is n e g l i
g i b l e c o m p a r e d to c o b a l t a c c o r d i n g to m a r k e r s t u d i e s
and
t o s t a b l e o x y g e n i s o t o p e d i f f u s i o n s t u d i e s ( JÔ JJL)
Thus
w h e n c o b a l t is o x i d i z e d , t h e m i g r a t i n g s p e c i e s s h o u l d b e
cobalt v i a cation vacancies and electrons (as electron
holes).
F o r an oxide g r o w i n g on a m e t a l by a bulk diffusion c o n
trolled process,
C. Wagner ( 4 ) derived an expression for
the
flux as
eq
c m sec
z
RT
F
f
P
(t
1 +
t )t q
2
| |
2
u
p
ffOj
P Q

<
3. W A G N E R
High-Temperature
Corrosion
83
Journal of Metals
Figure 5. Tracer diffusion in cobaltous oxide as a function of oxygen pressure
[and hence Co/O ratio given by Equations 9 and 13]. The symbols (X) denote
data obtained by a sectioning technique while () denote data by the surface
decrease method. The slopes of the lines are approximately one-fourth, indicating
the existence of singly ionized cation vacancies (6).
Journal of Physics and Chemistry of Solids

Figure 6. Electronic conductivity of cobaltous oxide single cry stab as a function
of oxygen pressure. The slopes of the lines are approximately one-quarter, indi
cating the eixstence of singly ionized cation vacancies and compensating electron
holes (7).

84
w h e r e t h e f l u x n / A is t h e r a t e o f o x i d e f o r m a t i o n p e r u n i t a r e a ,
F is F a r a d a y ' s c o n s t a n t , N
is A v o g a d r o s n u m b e r , q is t h e
e l e c t r o n i c c h a r g e , t d e n o t e s a t r a n s f e r e n c e n u m b e r a n d the s u b
s c r i p t s 1, 2 a n d 3 d e n o t e t h e m e t a l i o n , t h e o x y g e n i o n a n d
e l e c t r o n , r e s p e c t i v e l y . T h e t o t a l e l e c t r i c a l c o n d u c t i v i t y is .
L o c a l e q u i l i b r i u m is a s s u m e d t o o c c u r at t h e m e t a l - o x i d e i n t e r
f a c e a n d a l s o at t h e o x i d e - g a s i n t e r f a c e . T h e r e f o r e , t h e c h e m i
c a l p o t e n t i a l o f o x y g e n is f i x e d at e a c h i n t e r f a c e . T h e o x y g e n
p r e s s u r e at t h e m e t a l - o x i d e i n t e r f a c e is f i x e d a s t h e d i s s o c i a
t i o n p r e s s u r e of the o x i d e a n d d e n o t e d a s P o T h e o x y g e n
p a r t i a l p r e s s u r e in t h e g a s p h a s e , p 5 > is at e q u i l i b r i u m at t h e
o x i d e - g a s i n t e r f a c e . ( S e e F i g u r e 7) T h i s e q u a t i o n m a y be
written as
k
Q
A
"
w h e r e k is t h e r a t i o n a l r a t e c o n s t a n t * e x p r e s s e d a s e q / c m - s e c .
I n o t h e r w o r d s , t h e f l u x is i n v e r s e l y p r o p o r t i o n a l t h e f i l m
t h i c k n e s s - - j u s t the r e q u i r e m e n t of the p a r a b o l i c r a t e l a w .
When t
t i o r t , ( t h e o x i d e is p r i m a r i l y a n e l e c t r o n i c c o n
d u c t o r ) the e q u a t i o n m a y be r e w r i t t e n u s i n g the N e r n s t - E i n s t e i n
equation,
r
D =
u.
B. kT = iV- kT.
|z.|q
(17)
H e r e B ^ is t h e a b s o l u t e m o b i l i t y o f t h e i t h s p e c i e s , u^ t h e d r i f t
m o b i l i t y , D f the s e l f d i f f u s i o n c o e f f i c i e n t a n d the other t e r m s
h a v e t h e i r u s u a l s i g n i f i c a n c e . It f o l l o w s t h a t
w h e r e C q d e n o t e s the n u m b e r of e q u i v a l e n t s of o x i d e p e r c c .
P a r t i c u l a r n o t e is m a d e o f t h e f a c t t h a t t h e t r a n s p o r t n u m b e r s
a n d the d i f f u s i o n c o e f f i c i e n t s a r e b e h i n d the i n t e g r a l b e c a u s e
the p a r a m e t e r s depend d e c i s i v e l y o n the m e t a l - t o - o x y g e n r a t i o
a n d h e n c e o n the e f f e c t i v e v a l u e of the o x y g e n p o t e n t i a l . T h e
v a l e n c e of the c a t i o n and a n i o n , z a n d z a r e b e h i n d the i n t e
gral.
e
T h e r a t i o n a l r a t e c o n s t a n t , 1 ^ , is r e l a t e d t o t h e T a m m a n
rate constant,
k
= k^/v.
1
(See footnote on Page
2)

3.
WAGNER
High-Temperature
Corrosion
85
F r e q u e n t l y , the v a l u e s of a n d D
are very dissimilar
a n d o n e t e r m in b r a c k e t s E q . ( 1 8 ) m a y b e n e g l e c t e d .
For
e x a m p l e , in t h e c a s e o f t h e o x i d a t i o n o f c o b a l t , i t w a s n o t e d
e a r l i e r t h a t D D Q in C o O . C o n s e q u e n t l y , t h e s e c o n d t e r m
in b r a c k e t s m a y b e n e g l e c t e d a n d
(19)
O f t e n a u t h o r s p l o t the l o g a r i t h m of the p a r a b o l i c r a t e c o n s t a n t ( u s u a l l y k p o r fop) v e r s u s l o g P Q a n d i n f e r f r o m t h e
oxygen p r e s s u r e dependence ( 1/n) a m e c h a n i s m .
If o n e m e c h a n i s m d o m i n a t e s a c r o s s t h e o x i d e l a y e r , t h a t is, o n e m e c h a n i s m
is p r e d o m i n a t e b e t w e e n P Q ' a n d t h e u p p e r l i m i t f o r P Q ^ , t h e n
2
1_
[
0
J_
( 2 0 )
w h e r e the v a l u e o f a n d i t s s i g n w i l l d e p e n d o n t h e t y p e o f d e
f e c t s in t h e o x i d e .
F o r p-type oxides s u c h as cobaltous o x i d e ,
1/n = + 1/ 4 , for cuprous oxide 1/n = + 1/8, etc.
F o r an n-type
oxide such as Z n O , P Q
~ /
D e t a i l s of the d e f e c t s t r u c t u r e
o f m a n y c o m p o u n d s m a y be f o u n d , f o r e x a m p l e , in t h e b o o k b y
K r o g e r ( 12).
N o t e t h a t a n I n c r e a s e in o x y g e n p r e s s u r e (po
) r e s u l t s in
a n i n c r e a s e in o x i d a t i o n r a t e . H o w e v e r t h e s i g n o f t h e e x p o n e n t
o n t h e o x y g e n p r e s s u r e in E q . ( 2 0 ) e x e r t s a l a r g e e f f e c t .
For
c o b a l t o u s o x i d e , 1/n = + 1/4.
A n i n c r e a s e in o x y g e n r e s u l t s in
a n i n c r e a s e in t h e c o n c e n t r a t i o n o f c a t i o n v a c a n c i e s a n d a c o n
s e q u e n t i n c r e a s e in o x i d a t i o n r a t e . B u t f o r s o m e m e t a l s , t h e
c h a n g e in o x i d a t i o n r a t e w i t h o x y g e n p r e s s u r e is s m a l l .
For
example, zinc oxide growing on zinc m e t a l . The dominant de
f e c t s in z i n c o x i d e a r e s i n g l y i o n i z e d z i n c i n t e r s t i t i a l s a n d c o m
p e n s a t i n g e l e c t r o n s ( i . e. , Z n / O > 1 ) . T h e e q u a t i o n m a y be
written as
=
ZnO = Zn* + e'
+ 1/2 0 .
The corresponding e q u i l i b r i u m constant

K
= [Zn!][e']
(21)
p i
u
and electroneutrality condition
is
(22)
is
[Zn:]=[e']

(.23)
86
so that
[']
=/K
2 2
(24)
2
H e n c e , i n c r e a s i n g the o x y g e n p r e s s u r e o v e r z i n c o x i d e g r o w i n g
o n z i n c m e t a l a f f e c t s the o x i d a t i o n r a t e v e r y l i t t l e b e c a u s e d i s f u s i o n t h r o u g h z i n c o x i d e is v i a i n t e r s t i t i a l z i n c i o n s .
These
l i m i t i n g c a s e s a r e s h o w n s c h e m a t i c a l l y in F i g u r e 8 ( 1 3 ) ,
T h e t e m p e r a t u r e d e p e n d e n c e o f t h e k i n e t i c s at c o n s t a n t
o x y g e n p r e s s u r e is o f t e n p l o t t e d a s l o g k p o r l o g krp v e r s u s
1/T.
In a d d i t i o n to the m i g r a t i o n e n t h a l p y of the m o b i l e s p e c i e s , the
s l o p e of s u c h a n A r r h e n i u s p l o t m a y r e f l e c t a n e n t h a l p y f o r the
c h a n g e in c o m p o s i t i o n o f t h e o x i d e w i t h t e m p e r a t u r e .
The oxidation rat
self diffusion data. C o n v e r s e l y
to c a l c u l a t e s e l f d i f f u s i o n d a t a . E q . ( 18) m a y be r e a r r a n g e d
a n d the r a t e c o n s t a n t d i f f e r e n t i a t e d w i t h r e s p e c t to l o g o x y g e n
p r e s s u r e to y i e l d
CrfhD?
'
I
} =
f ^
eq
(25)
d l n
P<D
Di
Moreover
When
and z i = z
, the e q u a t i o n m a y be s i m p l i f i e d .
the p r a c t i c a l s c a l i n g c o n s t a n t s m a y be
into E q . (25) to y i e l d
s
P
D
= constant
d log
d
introduced
(26)
T h u s i f o n e m e a s u r e s k p ( o r k-p ) a s a f u n c t i o n o f o x y g e n p r e s
s u r e a n d p l o t s the data a s k p ( o r krp) v e r s u s l o g P Q * , the t a n
g e n t t o t h e c u r v e g e n e r a t e d y i e l d s a v a l u e o f D at a n y f i x e d
PQ S u c h p r o c e d u r e s h a v e b e e n u s e d b y F . S. P e t t i t [ F e O
( l l ) ] , K . F u e k i a n d J. B . W a g n e r [ N i O ( 1 5 _ ) , M n O ( 1 6 ) ] a n d
b y S . M r o w e c a n d c o w o r k e r s [ C o O (17_, 1 8 ) , C u ( 1 9 ) ] .
The
a g r e e m e n t b e t w e e n s e l f d i f f u s i o n data c a l c u l a t e d f r o m d i r e c t
r a d i o t r a c e r d i f f u s i o n data and those c a l c u l a t e d f r o m o x i d a t i o n
k i n e t i c s is r e m a r k a b l y g o o d i n d i c a t i n g t h e v a l i d i t y o f C .
Wagner's theory.
x
7 7
S o m e m e t a l - o x y g e n s y s t e m s e x i s t w i t h m o r e than one
stable oxide compound.
E x a m p l e s a r e C o O and C o 0 ; F e O ,
Fe 0
and F e 0 ; and C u 0 and C u O . When oxygen p r e s s u r e s
h i g h enough to n u c l e a t e a s e c o n d p h a s e a r e e n c o u n t e r e d ,
the
r a t e of o x i d a t i o n m a y be a l t e r e d d r a m a t i c a l l y . A s a n e x a m p l e ,
3

3. W A G N E R
High-Temperature
METAL
Corrosion
OXIDE
87
0 GAS
2
-oxygen onsFigure 7. Schematic of transport processes through an oxide layer growing on a

metal. Two limiting cases may be distinguished. First, metal ions and electrons
may migrate from the metal toward the oxide-gas interface and second, oxygen
ions may migrate toward the
the opposite direction. In any volume element of the oxide, electrical neutrality
is required. The chemical potential of oxygenisfixedatboth the metaloxide and
the oxide-gas interface. The former is fixed by the dissociation pressure of the
oxide, po ', and the htter by the ambient oxygen partial prsure, po "2
METAL
GAS
Figure 8. Schematic of the effect of

oxygen partial pressure on the concentration of defects in a oxide growing via
parabolic oxidation on a metal.
metal
deficit
GAS
The upper figure shows the effect of increasing oxygen pressure on a metal deficit
oxide, e.g., cobaltous oxide. See Equations
9, 10, 11, 12, and 13. The lattice defects in
CoO are V '. Parabolic oxidation proceeds
via diffusion of cobalt ions migrating by
means of V '. Thus increasing p " exerts
a large influence on the oxidation rate of
cobalt. The lowerfigureshows the effect of
oxygen partial pressure on a metal excess
oxide growing on a metal, e.g., zinc oxide.
The lattice predominant defectsinZnO are
Z n / . See Equations 21, 22, 23, and 24.
Hence increasing the oxygen pressure does
not appreciably affect the oxidation rate (13).
Co
Vo

02
CORROSION
88
CHEMISTRY
c o n s i d e r the o x i d a t i o n o f p u r e c o p p e r t o c u p r o u s o x i d e .
The
r a t e of o x i d a t i o n i n c r e a s e s w i t h i n c r e a s i n g o x y g e n p r e s s u r e
u n t i l t h e c u p r i c o x i d e p h a s e is f o r m e d o n t o p o f t h e g r o w i n g
cuprous oxide.
In t h i s e x a m p l e o x i d a t i o n p r o c e e d s v i a d i f f u s i o n
of c o p p e r ( v i a s i n g l y i o n i z e d c o p p e r i o n v a c a n c i e s ) t h r o u g h the
inner oxide.
When P Q
a t t a i n s the v a l u e f o r the c o e x i s t e n c e of
C u O a n d C u O , t h e g r a d i e n t in o x y g e n a c t i v i t y a n d c a t i o n v a c a n
c y c o n c e n t r a t i o n is f i x e d ( P Q ' e q u a l s t h e d i s s o c i a t i o n p r e s s u r e
f o r C u 0 or the c o e x i s t e n c e o x y g e n p r e s s u r e f o r C u a n d C u 0 ) .
T h e v a l u e o f t h e o x y g e n p r e s s u r e at t h e C u 0 - C u O b o u n d a r y is
f i x e d a n d b e c a u s e d i f f u s i o n o f c o p p e r t h r o u g h t h e C u 0 is r a t e
l i m i t i n g , t h e k i n e t i c s b e c o m e i n d e p e n d e n t o f o x y g e n p r e s s u r e at
t h i s p o i n t . T h i s s i t u a t i o n is s h o w n s c h e m a t i c a l l y in F i g u r e 9 .
O x i d a t i o n of a l l o y s i n t r o d u c e s a h i g h e r d e g r e e of c o m
p l e x i t y . W h e n t w o c o m p o n e n t s a r e p r e s e n t , e a c h is c o m p e t i n g
f o r t h e o x y g e n in a c c o r
o x i d e p e r g r a m a t o m of o x y g e n .
F o r illustrative purposes, con
sider again limiting cases.
T h e f i r s t is a b i n a r y a l l o y , A B ,
w h i c h is v e r y d i l u t e in o n e c o m p o n e n t , e . g . , 9 9 . 5 at $ A a n d
0 . 5 at $ B . F u r t h e r m o r e , a s s u m e t h e r e s p e c t i v e o x i d e s , A O
a n d B O f o r m s o l i d s o l u t i o n s . S u c h a l l o y s of n i c k e l h a v e b e e n
e x t e n s i v e l y s t u d i e d . W h e n n i c k e l c o n t a i n i n g s m a l l a m o u n t s of
c h r o m i u m is o x i d i z e d , t h e o x i d a t i o n k i n e t i c s a r e m o r e r a p i d t h a n
for pure nickel.
T h e r e a s o n is t h a t t h e s m a l l a m o u n t o f c h r o m
i u m e n t e r s the n i c k e l o x i d e c r e a t i n g a g r e a t e r c o n c e n t r a t i o n of
n i c k e l i o n v a c a n c i e s w h i c h in t u r n i n c r e a s e s t h e d i f f u s i o n o f
n i c k e l a n d h e n c e t h e p a r a b o l i c o x i d a t i o n k i n e t i c s (20_).
The
relevant equations a r e as follows.
F o r p u r e n i c k e l o x i d e the
d e v i a t i o n f r o m s t o i c h i o m e t r y is s i m i l a r t o t h a t f o r c o b a l t o u s
o x i d e e x c e p t t h a t d o u b l y i o n i z e d c a t i o n v a c a n c i e s f o r m in p u r e
N i at e l e v a t e d t e m p e r a t u r e s .
2
+ 2h\
(27)
;]*/p f.
(28)
The electroneutrality condition
is
(29)
so that
t

(30)
3. W A G N E R
T
or
kp
k
High-Temperature
Corrosion
CUgO
89
Cu 0 + CuO
<
dissoc. pressure
of CuO - Cu^P
log R "
>
Figure 9. Schematic of the behavior of the parabolic rate constant as a function

of oxygen pressure for the oxidation of copper. The rate increases [1/n == 1/8, see
Equation 20] until the formation of CuO occurs. At that point the chemical poten
tials of oxygen are fixed both at the Cu-Cu 0
and at the Cu 0-CuO
interface,
and the kinetics become independent of external oxygen pressure (13).
2

CORROSION
90
F o r a fixed oxygen p r e s s u r e , adding a donor ( C r ^ )

the c o n c e n t r a t i o n of c a t i o n v a c a n c i e s a c c o r d i n g to
C
^ 3 =
N i
increases
N i
CHEMISTRY
a c c o r d i n g l y the o x i d a t i o n r a t e i n c r e a s e s ( 2 ) .
Conversely*
a d d i n g a n a c c e p t o r ( L i ^ ) d e c r e a s e s the c o n c e n t r a t i o n of c a t i o n
v a c a n c i e s and the r a t e d e c r e a s e s ' * ( 2 ) .
S u c h m o d i f i c a t i o n of
o x i d a t i o n k i n e t i c s h a s b e e n t e r m e d the d o p i n g e f f e c t by a l i o v a l e n t a d d i t i o n s . T h e d e f e c t c h e m i s t r y ( n u m b e r a n d t y p e s of
lattice and electronic defects) has been tested u s i n g chiefly e l e c
t r i c a l c o n d u c t i v i t y but a l s o t h e r m o g r a v i m e t r y a n d d i f f u s i o n
studies on doped c r y s t a l s . T h e technique has been used e x t e n
s i v e l y a n d q u a n t i t a t i v e p r e d i c t i o n s c a n be r e a d i l y m a d e p r o v i d e d
t h e d e f e c t s t r u c t u r e o f t h e h o s t l a t t i c e is k n o w n . F o r e x a m p l e ,
in t h e c a s e o f n i c k e l c o n t a i n i n
k (Ni-Cr
p
alloy)
k (pure Ni)
' = const.
m o l e f r a c t i o n C r * . in d o p e d N i O
1
.
m o l e f r a c t i o n h in p u r e N i O
T
<*
(32)
T h i s h o l d s f o r d i l u t e a l l o y s a n d d i l u t e s o l i d s o l u t i o n of o x i d e s .
If h i g h e r c o n c e n t r a t i o n s o f c h r o m i u m a r e u s e d , a s e c o n d p h a s e
of C r 0
m a y f o r m on the outer s u r f a c e .
Consequently,a situa
t i o n s i m i l a r to t h a t d i s c u s s e d a b o v e f o r the f o r m a t i o n of C u O o n
C u 0 obtains. However, transport through C r 0
is v e r y s l o w
and that step b e c o m e s r a t e l i m i t i n g w i t h a c o n c u r r e n t d r a m a t i c
d e c r e a s e in o x i d a t i o n r a t e o f t h e a l l o y .
2
A n o t h e r l i m i t i n g c a s e is t h a t o f a n a l l o y , A B , w h i c h
o x i d i z e s t o f o r m o n l y o n e o x i d e , A O . A n e x a m p l e is t h e n i c k e l platinum alloy.
P l a t i n u m d o e s n ' t o x i d i z e a n d o n l y N i O is
formed.
W h e n a g i v e n a l l o y is o x i d i z e d at h i g h t e m p e r a t u r e s ,
t h e f o r m a t i o n o f N i O u s e s u p t h e n i c k e l in t h e s u r f a c e o f t h e
alloy.
M o r e n i c k e l m u s t d i f f u s e to the s u r f a c e f r o m the b u l k of
t h e a l l o y in o r d e r t o f o r m m o r e N i O . S i m u l t a n e o u s l y , p l a t i n u m
T h e p r e p a r a t i o n o f a L i - N i a l l o y is e x c e e d i n g l y d i f f i c u l t o w i n g
to v a p o r i z a t i o n p r o b l e m s .
The theory has been tested by
v a p o r i z i n g L i onto the g r o w i n g N i O as N i w a s o x i d i z e d .
A
d e c r e a s e in o x i d a t i o n r a t e w a s o b s e r v e d . (2 )
2

3.
WAGNER
High-Temperature
91
Corrosion
m u s t diffuse a w a y f r o m the s u r f a c e ( s e e F i g u r e 10).

The
c h e m i c a l p o t e n t i a l o f o x y g e n at t h e a l l o y - o x i d e i n t e r f a c e is n o t
f i x e d but c h a n g e s s l o w l y w i t h t i m e a s the c o m p o s i t i o n of the
a l l o y c h a n g e s a c c o r d i n g to
Ni (in alloy) + J 0
= NiO
(33)
Ni Of
T h e N i O is p u r e s o i t s a c t i v i t y is s e t e q u a l t o u n i t y in
Eq. (34).
H o w e v e r the a c t i v i t y of n i c k e l , a ^ , d e c r e a s e s w i t h
t i m e ( t h e a l l o y b e c o m e s m o r e c o n c e n t r a t e d in P t ) s o t h e o x y g e n
p a r t i a l p r e s s u r e at t h e a l l o y - N i O i n t e r f a c e i n c r e a s e s w i t h t i m e
(see E q . (34)j T h i s effec
c h a n g e in o x y g e n p r e s s u r
P Q / constant).
F u r t h e r m o r e , different alloys w i l l oxicnze
at d i f f e r e n t r a t e s .
F o r a l l o y s r i c h in n i c k e l , t h e k i n e t i c s w i l l
b e a l m o s t t h o s e o f p u r e n i c k e l . B u t a s t h e c o n c e n t r a t i o n of
p l a t i n u m i n c r e a s e s b e y o n d a c e r t a i n c r i t i c a l v a l u e , d i f f u s i o n of
n i c k e l to the m e t a l - m e t a l o x i d e s u r f a c e w i l l be r a t e - d e t e r
m i n i n g a n d a l a r g e d e c r e a s e in o x i d a t i o n r a t e w i l l o c c u r , i . e . ,
t h e r a t e l i m i t i n g s t e p w i l l b e d i f f u s i o n in t h e a l l o y a n d n o t d i f
f u s i o n t h r o u g h the oxide s c a l e .
a
A n o t h e r l i m i t i n g c a s e is a n a l l o y , A B , n e i t h e r c o m p o n e n t
o f w h i c h i n i t i a l l y r e a c t s t o f o r m a n e x t e r n a l s c a l e a n d in w h i c h
component A has a m u c h greater affinity for oxygen than B . A
c l a s s i c a l e x a m p l e is t h e s i l v e r - i n d i u m a l l o y s y s t e m .
Silver
d o e s n ' t f o r m a n o x i d e at e l e v a t e d t e m p e r a t u r e s , b u t i t d o e s
dissolve oxygen.
S m a l l a m o u n t s of i n d i u m w i l l t h e r e f o r e f o r m
a n o x i d e w i t h i n the a l l o y m e t a l , a s o - c a l l e d s u b s c a l e o r i n t e r n a l
oxide.
T h e p r o c e s s is d i f f u s i o n c o n t r o l l e d a n d t h e d i f f u s i o n o f
o x y g e n in t h e a l l o y is r a t e l i m i t i n g .
Such systems have been
s t u d i e d e x t e n s i v e l y by R . A . R a p p , e s p e c i a l l y the t r a n s i t i o n
f r o m o n l y i n t e r n a l o x i d a t i o n to the f o r m a t i o n of a n e x t e r n a l
scale (22).
W h e n both c o m p o n e n t s of a h o m o g e n e o u s , one p h a s e a l l o y
r e a c t w i t h o x y g e n , t h e r e is a c o m p e t i t i o n f o r t h e o x y g e n in
t e r m s of the a f f i n i t y f o r o x y g e n a s m e n t i o n e d a b o v e .
If t h e
o x i d e s s o f o r m e d a r e i m m i s c i b l e , the n u c l e a t i o n a n d g r o w t h of
e a c h o x i d e p h a s e a s w e l l a s d i s p l a c e m e n t r e a c t i o n s m u s t be
considered.
A s a n e x a m p l e , c o n s i d e r 8 5 - 1 5 b r a s s (85 wt $
c o p p e r = 15 w t $ z i n c ) o x i d i z e d at 7 0 0 C . F o r t h e f i r s t h o u r
t h e k i n e t i c s a r e n e a r l y p a r a b o l i c , i . e. , d i f f u s i o n c o n t r o l l e d .

92
T h e f r e e e n e r g y o f f o r m a t i o n f o r z i n c o x i d e is m u c h m o r e n e g a tive than that for c u p r o u s oxide.

B u t t r a n s p o r t of i o n s t h r o u g h
C u 0 is m u c h g r e a t e r t h a n t r a n s p o r t t h r o u g h Z n O .
Consequentl y , cuprous oxide and some z i n c oxide f o r m s on this b r a s s and
as time proceeds, a displacement reaction occurs
(23),
Z n (alloy) + C u 0 (oxide l a y e r ) = Z n O (oxide l a y e r ) +
2 Cu (free).
T h i s is i n d i c a t e d b y t h e a p p e a r a n c e o f f r e e c o p p e r
( p i n k c o l o r ) in t h e c r o s s s e c t i o n s o f t h e s a m p l e s a n d a d e c r e a s e
in r a t e a s m o r e Z n O f o r m s w i t h t i m e . F u r t h e r m o r e , i f t h e
o x y g e n is p u m p e d o u t o f t h e r e a c t i o n c h a m b e r a n d t h e s a m p l e
g i v e n a n a n n e a l in a n i n e r t g a s , t h e s u b s e q u e n t o x i d a t i o n k i n e t i c s in o x y g e n a r e d r a s t i c a l l y r e d u c e d ( s e e F i g u r e 1 1 ) .
This
l a r g e r e d u c t i o n in o x i d a t i o n k i n e t i c s is d u e to t h e l a r g e p r o p o r t i o n o f Z n O f o r m e d d u r i n g t h e a n n e a l in a n i n e r t g a s a n d t h e
f a c t t h a t d i f f u s i o n t h r o u g h Z n O is s l o w .
T h e i m p o r t a n c e of d i s p l a c e m e n t r e a c t i o n is
n a l g a s a t m o s p h e r e c a n g r o w by m e a n s of a d i s p l a c e m e n t
reaction.
A s m o r e and m o r e demands are placed on m a t e r i a l s for
e n e r g y p r o d u c t i o n , the d i v e r s i t y of c o r r o s i v e a t m o s p h e r e s
c o m p l i c a t e s and a c c e n t u a t e s the c o r r o s i o n p r o b l e m s .
For
e x a m p l e in c o a l g a s i f i c a t i o n p l a n t s a n d in c e r t a i n a i r p l a n e t u r b i n e e n g i n e a p p l i c a t i o n s , m i x t u r e s of o x y g e n a n d s u l f u r b e a r i n g
gases are encountered.
C o n s i d e r a p u r e m e t a l e x p o s e d to a
m i x e d o x i d a n t , e . g . , n i c k e l e x p o s e d to o x y g e n a n d s u l f u r
d i o x i d e . T h e s u l f u r d i o x i d e i n c r e a s e s the r a t e of p a r a b o l i c
corrosion.
One l i m i t i n g case has been d i s c u s s e d by A l c o c k ,
Hockings and Steele (24).
T h e y suggested that s u l f u r entered
N i O and created additional cation vacancies which increased
t h e o x i d a t i o n r a t e o f n i c k e l . J. B . W a g n e r (25) s u g g e s t e d t h e
following equation,
2
S0 (g) = SQ(inNiO) +0
2
+e'
(35)
a n d t h a t i f s u l f u r a c t s a s a d o n o r , i t a f f e c t s N i O in t h e s a m e
w a y a s c h r o m i u m d o p i n g , i . e. , c r e a t e s c a t i o n v a c a n c i e s .
H o w e v e r , t h e s o l u b i l i t y o f s u l f u r is v e r y s m a l l [ a b o u t 1 0 / c c
(26_)1 a n d s o m e r e p o r t e d i n c r e a s e s in r a t e s w e r e f a r in e x c e s s
of that w h i c h E q . ( 3 5 ) c o u l d a c c o u n t f o r .
W o r r e l l (27) m a d e a
v e r y important suggestion.
In S 0 - 0
gas m i x t u r e s , it s o m e t i m e s h a p p e n s that two p h a s e ( d u p l e x ) s c a l e s a r e f o r m e d .
T h e s e s c a l e s c o n s i s t of t h i n c h a n n e l s o r s t r i n g e r s of s u l f i d e
e m b e d d e d in a m a t r i x o f o x i d e .
B e c a u s e d i f f u s i o n in t h e s u l f i d e s is s o m u c h f a s t e r t h a n d i f f u s i o n in o x i d e s , t h e r a t e is
d e t e r m i n e d by d i f f u s i o n t h r o u g h the c h a n n e l s . T h i s t y p e of
1 8

3. W A G N E R
High-Temperature
Corrosion
93
Ni-R ALLOY
CONC.
Figure 10. Schematic of the concentration profile of nickelina Ni-Pt alloy being
oxidized to form NiO as a growing oxide scale. The concentration profile of
nickel ion vacancies in NiOisalso shown. In the example discussed, the rate
determining stepisthe diffusion of nickel from the bulk alloy to the surface (and
of platinuminthe opposite direction) rather than diffusion of nickel via vacancies
in NiO (13).

Figure 11. Schematic of the oxidation of 85 wt % Cu-15 wt % Zn at 700C.
Initially the kinetics are almost parabolic, and diffusion through a two-phase scale
(Cu 0 and ZnO) is rate determining. The displacement reaction, Zn (alloy) +
Cu 0 (oxide layer) = 2Cu (free) - f Z n O (oxide layer), proceeds continuously. An
interrupted annealinargon allows the displacement reaction to proceed without
the uptake of further oxygen from the ambient. Subsequent oxidation proceeds
very slowly (23).
2

94
p a r a l l e l d i f f u s i o n p a t h w i l l be v e r y i m p o r t a n t in c o r r o s i o n o f
m u l t i p h a s e a l l o y s that f o r m m u l t i p h a s e s c a l e s .
In t h e f o r e g o i n g , l i m i t i n g c a s e s o f v a r i o u s h i g h t e m p e r a
ture, i s o t h e r m a l corrosion situations have been briefly d i s
cussed.
A c t u a l l y in m o s t e n g i n e e r i n g u s e s , t h e c o r r o s i o n is
n o t i s o t h e r m a l b u t i n v o l v e s c y c l i c t h e r m a l t r e a t m e n t ( e . g . , in
a turbine engine).
In a d d i t i o n to s e e k i n g a n o x i d e s c a l e that
w i l l e x h i b i t s l o w d i f f u s i o n o f t h e r e a c t a n t s , i t is n e c e s s a r y t h a t
the o x i d e r e s i s t t h e r m a l shockM o s t of the p r o t e c t i v e o x i d e s
involve A 1 0 , C r 0
or S i 0 .
E f f o r t s to i n c r e a s e the a d h e r
e n c e of the o x i d e on the m e t a l h a v e b e e n d i r e c t e d to a d d i t i o n s
of c e r t a i n r a r e e a r t h m e t a l o x i d e s to the m e t a l o r a l l o y .
These
o x i d e s a r e u s u a l l y i n s o l u b l e in b o t h t h e m e t a l a n d t h e o x i d e
scale.
S u r p r i s i n g l y , the s m a l l p a r t i c l e s of t h e s e a d d e d o x i d e s
often s e g r e g a t e to the
to p r o j e c t up f r o m th
i n c r e a s e in r e s i s t a n c e t o s p a l l i n g d u r i n g t h e r m a l s h o c k .
One
s u g g e s t i o n is t h a t t h e o x i d e p a r t i c l e s a c t a s " p e g s " t o p i n t h e
oxide scale.
O t h e r e x p l a n a t i o n s i n v o l v e c h a n g e s in t h e i n t e r
face c h e m i s t r y and concurrent adhesion between m e t a l and
s c a l e o r a c h a n g e in p l a s t i c i t y o f t h e o x i d e s c a l e .
In a n y c a s e
t h e e f f e c t is i m p o r t a n t a n d t h e m o s t a p p r o p r i a t e e x p l a n a t i o n
awaits s o m e challenging surface c h e m i s t r y and m i c r o a n a l y s i s .
T h e foregoing s u r v e y was focused on situations where
biilk diffusion p r o c e s s e s were rate determining.
Such systems
a r e a m e n a b l e to a n a l y s i s u s i n g a n e l e c t r o c h e m i c a l
approach.
Other factors such as transport down pores or c r a c k s , v o l a t i
l i z a t i o n o r m e l t i n g of the o x i d e s c a l e m a y o c c u r a n d r e q u i r e
d i f f e r e n t a n a l y s e s but d i f f u s i o n c o n t r o l l e d p r o c e s s e s m a y be
m a t h e m a t i c a l l y m o d e l e d and c o r r e l a t e d w i t h the defect c h e m
i s t r y of the c o r r o s i o n p r o d u c t .
These limiting cases provide
a g u i d e to u n d e r s t a n d i n g t h e m o r e c o m p l e x p h e n o m e n a f r e
quently encountered.
2
Literature Cited
1.
T a m m a n , G., Z. anong. und a l l g e m . C h e m i e , ( 1 9 2 0 )

111, 78.
2.
Pilling,
. B. and B e d w o r t h , R. E . , J. Inst. M e t a l s ,
( 1 9 2 3 ) 29, 529.
3.
Pfeil,
L. B., J. I r o n a n d S t e e l I n s t . , ( 1 9 2 9 ) 119, 501.
4.
Wagner,
C., Z. p h y s i k . C h e m i e , ( 1 9 3 3 ) B 2 1 , 25.
5. K r g e r , F. A. and V i n k , H. J., in " S o l i d State
Physics"
F.
S e i t z and D. Turnbull, e d s ) Academic Press, . Y.
1956.

3. WAGNER
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
95
High-Temperature Corrosion
C a r t e r , R. E . a n d Richardson, F. D., J. M e t a l s ( 1 9 5 4 )
6, 1244.
Eror,
N. G. a n d W a g n e r , J. . , Jr., J. P h y s . C h e m .
S o l i d s ( 1 9 6 8 ) , 29, 1597.
Carter,
R. E . a n d Richardson, F. D., J. M e t a l s ( 1 9 5 5 )
7, 336.
P e t t i t , F. S. and W a g n e r , J. . , Jr., Acta Metall. ( 1 9 6 4 )
12, 415.
C h e n , W. K. and J a c k s o n , R. . , J. P h y s . C h e m . S o l i d s
( 1 9 6 9 ) , 30, 1309.
H o l t , J. B., P r o c . Brit. C e r a m . Soc., ( 1 9 6 7 ) , 9, 157.
Krger, F. A . , "The Chemistry of I m p e r f e c t
Crystals,"
N o r t h H o l l a n d P u b l i s h i n g Co., Amsterdam, 1964.
W a g n e r , C., m i m e o g r a p h e d c o u r s e n o t e s , c o u r s e 3.63,
D e p a r t m e n t of Metallurgy,
P e t t i t , F. S., J. E l e c t r o c h e m
F u e k i , K. a n d W a g n e r , J. B., Jr., J. E l e c t r o c h e m . Soc.
( 1 9 6 5 ) , 112, 284.
F u e k i , K. a n d W a g n e r , J. B., Jr., J. Electrochem. Soc.
( 1 9 6 5 ) , 112, 970.
M r o w e c , S., Bull. A c a d . P o l o n . S c i . , S e r , Sci. C h i m .
( 1 9 6 7 ) , XV, 373.
M r o w e c , S., T. W a l e c a n d T. W e r b e r , Corrosion Sci.
( 1 9 6 6 ) , 6, 287.
M r o w e c , S. a n d Stoklosa, Bull. A c a d . P o l o n . Sci., S e r .
Sci. C h i m . ( 1 9 7 0 ) , X V I I I , 5 2 3 ; O x i d a t i o n of Metals, (1971)
3, 291.
P f e i f f e r , H. a n d H a u f f e , ., Z. M e t a l l k . ( 1 9 5 2 ) , 4 3 , 364.
H a u f f e , ., " O x i d a t i o n of Metals," English Translation by
K. Vorres, P l e n u m Press, . ., 1965.
R a p p , R. . , Corrosion, NACE ( 1 9 6 5 ) , 2 1 , 382.
L e v i n , R. L. a n d W a g n e r , J. B., Jr., J. E l e c t r o c h e m .
Soc. ( 1 9 6 1 ) , 108, 954.
A l c o c k , C. . , H o c k i n g , M. G. a n d Z a d o r , S.,
Corrosion
S c i . ( 1 9 6 9 ) , 9, 111.
W a g n e r , J. B., Jr., in " D e f e c t s and Transport in O x i d e s , "
(Seltzer,
M. S. a n d J a f f e e , R. I . , e d s . ) p. 283, P l e n u m
Press, . . , 1974.
C h a n g , D. R., Ph.D. Thesis, N o r t h w e s t e r n U n i v . 1973.
Worrell,
W. L . , lecture "The SO -O o x i d a t i o n of metals,"
p r e s e n t e d at the U. S. J o i n t S e m i n a r , " D e f e c t s and Dif
fusion in Solids," O c t o b e r 4-6, 1976, T o k y o , J a p a n , to be
published.
2
RECEIVED July 6, 1978.

4
Ionic and Electronic Conduction in Nonmetallic Phases
J O H N W.
PATTERSON
Engineering Research Institute and Department of Materials Science and Engineering,

Iowa State University, Ames, IA 50011
PART I
Open Circuit Theory and Parabolic Tarnishing Kinetics
Historical Background
About the turn of the century and shortly thereafter, certain
developments in mathematical physics and in physical chemistry
were realized which wer
and charge transport in
Smoluchowski(2) i n i t i a t e d the modern theory of Brownian motion
by idealizing it as a problem in random f l i g h t s . Then some seventeen years or so later, Joffee(3) proposed that i n t e r s t i t i a l defects could form inside the l a t t i c e of ionic crystals and play a
role in electrical conductivity. The f i r s t tenable model for ionic
conductivity was proposed by Frenkel(4), who recognized that vacancies and i n t e r s t i t i a l s could form internally to account for ion
movement.
Figure 1 is a schematic representation of Frenkel's notion:
an atom or ion can get dislodged from i t s normal site to form an
interstitial-vacancy pair. He further proposed that they do not a l ways recombine but instead may dissociate and thus contribute to
diffusional transport and e l e c t r i c a l conduction. They were free
to wander about in a "random walk" manner essentially equivalent to
that of Brownian motion... this meant they should exhibit a net
d r i f t in an applied f i e l d .
In the fluids considered by Einstein and Smoluchowski, a l l
species large and small are capable of substantial migration at a l l
times. In solid crystals, however, only the i n t e r s t i t i a l atoms and
those next to vacant sites can enjoy any significant amount of motion. Thus, i t was realized that the concentrations of mobile defects are the important things, at least in connection with the ionic
conductivity of crystals. An elaborate analysis of thermodynamic
equilibria of point defects was then developed by Wagner and
Schottky (5z_) in which the laws relating defect concentrations to impurities, ambient p a r t i a l pressures and temperature were worked out
in detail.
Wagner followed this in 1933 by combining v i r t u a l l y a l l the
foregoing concepts to explain the phenomenon of parabolic tarnishing of metal in aggressive environments ^ . He assumed that transport of neutral species was negligible compared to that of ions and
0-8412-0471-3/79/47-089-096$07.50/0

4.
PATTERSON
Conduction
in
Nonmetallic
Phases
-

Figure 1.
Frenkel defect in a crystal lattice

97
98
CORROSION
CHEMISTRY
electronic carriers, which no doubt must have seemed a rather bold

assumption to many others at that time. But beyond that he also
assumed that a l l the charged carriers migrated with Einstein-type
mobilities under the combined influences of free energy (i.e.,
chemical potential) gradients and electric f i e l d s . In this way,
he was able to transform the problem of parabolic scaling of metals to one of diffusional transport in a electrochemical medium.
The implication of Wagner's theory was that the parabolic
scaling rate constants, many of which were known for certain gasmetal combinations, should be quantitatively related to two basic
types of information.
A) Thermodynamic information, such as the formation free
energy for the scale and p a r t i a l pressure or a c t i v i t y data for
the environment... and
B) E l e c t r i c a l property information for the scaling compound,
such as e l e c t r i c a l conductivity
numbers or the open c i r c u i
In addition, the theory predicted that a measurable emf would
be established over the tarnishing layer, and moreover, that this
voltage could be used to infer the average ionic and electronic
transference numbers of the scale. Prior to Wagner's treatment,
of course, there had been no reason whatever to think that the
electrical properties of the scale compound should bear any relation to oxidation rates, nor was there any reason to think that
voltages should appear over these coatings.
And so the metal scaling systems known to exhibit parabolic
growth kinetics were soon selected for the c r i t i c a l testing of Wagner' s theory. The conductivity-emf-transference number data required by the theory were measured and the scaling rate constant
predicted. Then independent measurements of the same scaling constant were obtained, as for example from weight gain measurements
and the results compared.(10-12) . Astounding agreement was found and
much excitement began to spread in corrosion engineering c i r c l e s because Wagner's theory suggested many ways to possibly control or
stop scaling. But this optimism was somewhat overdone because so
few practical situations conform to the parabolic scaling prerequisites. Nevertheless, Wagner's theory has been applied and reviewed extensively and this continues up to the present time(13-19)
Presently, the major interest in Wagner's theory derives mainly
from the open c i r c u i t emf relationships rather than the scaling
rate predictions. Only a limited number of the metal scaling systems important to modern technology s t r i c t l y conform to the conditions required by Wagner's theory, because of various complicating factors (abrasion, thermal gradients, contaminations, and
so on). However, a variety of new solid electrolyte materials
has been developed for remote sensor applications(20) , fuel c e l l battery applications(20)
f
laboratory investigations of
thermodynamic data(21-23)^
-Q f these applications the solid
electrolyte element can be expected to perform according to
o r
I n

4.
PATTERSON
Conduction
in
Nonmetallic
99
Phases
Wagner's tarnishing theory but significant modifications are required for the non-open c i r c u i t c a s e s
) . in short, we can
say that the present understanding of solid-state electrochemistry
is largely due to Wagner's electrochemical theory of tarnishing
and moreover that the concepts as he i n i t i a l l y elucidated them
have remained in tact to the present time. In part II of this paper,
less simple mixed conducting phases and non open c i r c u i t conditions
w i l l be considered
2
Physical Processes Occurring During Parabolic Scaling

Patterson (19) has given a detailed discussion of Wagner's
theory complete with flow-diagram summaries for the derivations
of the quantitative formulas. But these derivations are much too
elaborate to develop here. We w i l l invoke a simplified model o r i ginally put forward by Hoar and Price (^ , but this comes later.
F i r s t l e t us outline th
in parabolic scaling.
Figure 2 f a c i l i t a t e s the physical description by showing the
compound M X^ (oxide, fluoride, chloride, etc.) attached as a
scaling layer to the substrate of metal M on the l e f t . The layer
is exposed to an atmosphere containing X 2 gas molecules ( O 2 , F ,
C l 2 f N / etc.) on the right where the X molecules become adsorbed
on the surface and eventually get incorporated as ions. Ultimately,
however, the scaling ratewhether measured by weight gains or
scale thicknesses is just the total assimilation
rate of X atoms by the scale.
This can happen in either of
two ways: by combining with cations which emerge at L or by d i f fusing in as anions.
For simplicity, assume for the moment that only cations are
mobile in the scale. Even though no X anions can move, adsorbed
X atoms can s t i l l be assimilated because M cations can migrate
from the other side to combine with the adsorbed gas atoms. Note
however, that the scale would grow only at the gas side in this
case. On the other hand, i f anions are mobile, but cations are
not, the adsorption-dissociation process X 2 (g)
2 X (ads) on the
right is followed by anion migration through the scale and growth
occurs at the M, M Xb interface (left side). These two situations
can be distinguished experimentally by identifying markers inside
the scale. The apparent change of depth of the marker with time
identifies the mobile ionic species.
If the scale is an ionic compound, X 2 molecules, which are
neutral, can be incorporated only as anions, which are negatively
charged X ions. Conversely, each incorporated M atom must become
a positively charged cation. This has important electrochemical
consequences because the region at L is forced to become increasingly electron-deficient or positively charged as the negative
anions are "formed" and then wander off toward the metal-rich side.
Similarly, the metal at the l e f t accrues a surplus of negative
charge due to the electrons liberated when M atoms enter the scale
as cations.
a

100
Eventually these oppositely charged outside layers cause a

very strong coulombic f i e l d to build up, but i t must be positive
on the gas side and negative at the metal side. But of course this
polarity necessarily opposes the migration of both anions and ca
tions and increasingly so as the charging continues to build.
That is, the incorporation of X atoms by the scale is self defeat
ing i f eletrochemical forces are at play . In fact, i f there were
no electronic leakage paths connecting the two surfaces, a l l cat
ion and anion migration would soon grind to a halt. At this point,
no further weight gain would be observed but an emf on the order
of volts would be observed.
However, some degree of internal shorting within scales always
occurs because scaling layers always exhibit at least a trace of
internal conduction by electronic carriers.
For this reason, i t
is best to think of scales as mixed (ionic and electronic) conduc
tors. The effect of the
charge,on the surfaces an
ingly. This would allow ionic migration to continue indefinitely
but at an ever-decreasing rate as the thickness of the scale in
creases. In principle then, real scaling layers never achieve the
completely arrested state alluded to above as a limiting case, in
stead, they thicken indefinitely but according to the parabolic
law. And since a l l the mobile species are presumed to be charged,
applied electric fields or currents can be used to significantly
alter the thickening kinetics and morphologies of mixed conducting
scaling systems.
Now i f the scale exhibits a large conductivity for electrons
(large compared to the ionic conductivity), massive internal short
ing occurs and no coulombic retardation of ion movement is possible.
In this situation, scaling proceeds as fast as the unhindered ions
can diffuse through the scale. And although the growth kinetics
w i l l s t i l l be parabolic, no perceptible open c i r c u i t emf w i l l be
found over the scaling layer. This is the limiting case in which
electronic conduction dominates in the scale. This limiting
case is at the opposite extreme to that in which ionic conduction
dominates, as discussed f i r s t .
Equivalent Circuit Description of Mixed Conduction in Solids
In essence chemical free energy differences cause the ions to
migrate during scaling. This is similar to the way batteries induce
current flow in resistors. In parabolic scaling the cations mi
grate outward to the gas surface while the anions move inwards to
ward the metal. The molar free energy (often called the chemical
potential) for the metal is highest at the metal side but very low
at the gas surface, and vice versa for the non metal species or
X.
Thus, every time a mole of metal migrates out from the inside/
the total free energy of the entire system drops by the amount
2
II
- u
=
M
M

4.
PATTERSON
Conduction
in
Nonmetallic
Phases
101
Here as elsewhere below, a double prime indicates the gas side at

L whereas a single prime quantity refers to the metal side at zero.
Thus, the free energy change of equation 1 is a drop because y is
very low compared to \x which prevails at the metal interface. By
the same token every mole of X passing in the opposite direction
changes the free energy inventory by
m
ii
h - h y
2
X 2
= -h
and is also a decrease as

refers to the gas side.
These free energy drops act as the chemical driving forces
which cause the ionic migrations to take place in the f i r s t place.
They continue to persist but become less and less effective as the
coulombic fields build up at the opposite sides of the scale. In
any case, we begin to see how an e l e c t r i c a l formulation of the
chemical process of scalin might becom possible
Th actual ion
ic migrations amount to
being driven at the expense o the chemica free energy inventory,
just as occurs when batteries discharge through a c i r c u i t of resis
tors.
A successful equivalent c i r c u i t approach to Wagner's theory
was worked out by Hoar and Price
They developed a simple volt
age divider c i r c u i t which gives quantitative formulas for emf and
scaling rate that are very similar to those derived more rigorously
by Wagner. A linear lumped version of their proposed c i r c u i t is
shown in Fig. 3. The subscripts 1, 2 and 3 refer to M cations, X
anions and electrons respectively.
The voltages
and V are given by the expressions
2
l = - V
= - h Ap
X 2
3
/Z F
Since the valences of the cations and anions are always opposite in
sign and the two chemical potential differences are always opposed
in scaling, i t follows that both voltages w i l l have the same sign.
As a matter of fact, i t can be shown that they are also of precisely
the same value for two component scales. This equality, which de
rives from the so called Gibbs-Duhem relation between -^ ^ ^2'
merely means that the two batteries
and V are equivalent to,
and hence may be replaced by, the single one shown dottedin on the
figure.
If voltages
and V simulate the chemical driving forces ac
ting on the ions during scaling, the resistors
and R simulate
the scale's resistance to cation and anion migration. Its imped
ance to electron flow is represented by the single resistor R 3
which is shown connected a l l the way across the scale thickness.
The resistor R 3 simulates the electronic leakage path which weakens
the coulombic fields and allows ion migration to continue indefi
nitely rather than halting. The usual definitional formulas hold
anc

102
SUBSTRATE
METAL M
AMBIENT ATMOSPHERE
(ACTUAL X GAS,
PARTIAL PRESSURE = p"
SCALING LAYER
ab
EFFECTIVE
CATIONS
X GAS
PARTIAL PRESSURE = Pi
I ANIONS J 2
ELECTRONS J -
Industrial and Engineering Chemistry,

Product Research and Development
Figure 2.
Physical arrangement of a metal (M) undergoing scaling (39)
Yl
iCATIONS
I !
-
1
CIRCUIT
ANALOG
OF SCALE
*ion
^2jANIONS
R
ELECTRONS
EXTERNAL
LEADS
- oSCALE EMF
Industrial and Engineering Chemistry,
Product Research and Development
Figure 3.
DC circuit analog to simulate scaling according to electrochemical

theory (39)

PATTERSON
4.
Conduction
in
Nonmetallic
103
Phases
for these resistors

R
i -
1 / G
i =
< = 1-2.3
1
Here R is in ohms, the conductance G; is in reciprocal ohms, L
and A are the scale's thickness (cm) and area (cm ), respectively,
and is the so called specific partial conductivity for species
i in the scale.
Keep in mind that we have not really justified the analog
circuit as a v a l i d way to describe the scaling process. As a
matter of fact a rigorous jiustification would probably be a very
d i f f i c u l t task involving some very knotty, philosophical, questions.
What one can do, however, is to proceed with the model on the tentative assumption that i t may work and thus derive as many useful formulas as possible to see how they square with Wagner's more rigorous ones and with experimenta
Hoar and Price did and indee
with relatively l i t t l e effort by using their idea. We w i l l exploit their approach here rather than trying to go through Wagner's
more rigorous development, but i t is worth mentioning that Wagner
himself expressed reservations about the Hoar-Price paper. This
appears in the discussion section that followed their presentation
before the Faraday Society(5).
Let us consider the open c i r c u i t emf that occurs in scaling.
A f a i r l y straightforward dc c i r c u i t analysis of Figure 3 leads to
the following formula
= [t-L + t ]V
6
2
Here V is the so called thermodynamic voltage and from Equation 4

is found to be
RT
/ '
V
2Z F In
2
2
2
Px2 is that of the gas atmosphere while 1 which prevails at the M,

a b interface, is determined by the standard formation free energy
AG| for M Xfc. The formula is
2
" 2 = exp (2AG/bRT)

x
which comes from thermodynamics. The t's are fractional conduct

ances and are called transference numbers. When the common L/A
factors are cancelled, they take the form
3
fc
i =
V E1
j =
The demoninator here is simply the total electrical conductivity

of the scale. It follows from the way they are defined that
the transference numbers summed over a l l the species must always
add up to unity. Accordingly the so called ionic transference

104
number is related to the electronic one t3 in the following way

t.
= t_ + t
ion
1 2
= 1 - t
10
Now Wagner's expression for the open c i r c u i t emf is

[
This appears to be rather different from the Hoar-Price formula

given in Equation 6 above, but actually they are almost the same
thing. To see the very close similarity we must f i r s t realize that
we applied the dc c i r c u i t analog to the whole scale. But point to
point variations in the conductivities and hence transference num
bers are possible. Hence, we must apply the analog to each d i f
ferential thickness and add the results because they are a l l joined
together in series to make up the total scale thickness
With this
in mind the emf for eac
i.e.,
dE =
+ t ]dV
12
where the t values apply only to the element in question. To ob

tain the overall emf we simply add the contributions from every
location in the scale. But note that Equation 4 implie-s
dV = - h d y / Z F
X2
13
and that the summing of differential increments amounts to nothing

more than integrating. Hence, the Hoar-Price equivalent c i r c u i t
expression for should really have been written
=
[t_ + t J d V
Jo
14
-L
But this is v i r t u a l l y identical to Wagner's formula when Equation 13

for dV is considered. In this situation however, the d i f f e r e n t i a l
resistors which enter into t-^ and t are conceived to vary in value
according to the local "voltage", which is unlikely for resistors
of any sort. However, we can imagine ways in which the values
could depend on the local Mx value in a crystal and this is what
is really to be done when applying the Hoar-Price approach.
The scaling rate at a given instant can be readily calculated
from the sum of the two ionic currents as follows. Assimilation
due to the a r r i v a l of cations at L would be I/ZjF multiplied by
b/a. This must be added to the moles of X that permeate through
the scale and this would be -I /Z F. Adding these together and
noting the v i r t u a l stoichiometry constraint that Zâ+Z b = 0, we
arrive at
2
x = [Ii + I ] /Z F
2

15
PATTERSON
4.
Conduction
in
Nonmetallic
105
Phases
Here, is the total molar acquisition rate of X atoms from the

gas atmosphere. But from an analysis of the c i r c u i t in Figure 3,
the following can be shown
E / R
"
1 6
where is the open c i r c u i t emf discussed e a r l i e r . But here again

the circuit analysis should be applied to each d i f f e r e n t i a l ele
ment because of point-to-point variations through the scale. When
this is done, the and L in Equation (16) become dE and d l , respec
tively, so that Equation (15) can now be written as
dE
n
x -
/ Z
Separating variables, integrating and solving for
1 7
then gives
This is to be compared with Wagner's expression for the same quan

t i t y which for this case would be
where is the total conductivity of the scale. But these two

formulas are again v i r t u a l l y identical because -^ = t3 by de
f i n i t i o n and because of Equation 13 for dV.
Summarizing the situation concerning equivalent c i r c u i t model
ling, we cay say that this is a very useful approach and i t leads
to accurate results and insights i f the proper precautions are
taken. I think the day w i l l come soon when the theory of mixed
conduction w i l l have to be considered in great detail a l l over
again. For example, i f s o l i d electrolyte fuel cells and hydrolysis
systems are built, their performance characteristics w i l l to a
large extent be dictated by mixed conduction processes that take
place inside them during operation. It is my view that the equi
valent circuit modelling approach-with proper precautions taken
w i l l prove to be the most expedient way to extend Wagner's to
such closed circuit applications. Keep in mind that the entire
development given above applies only to open c i r c u i t conditons.
Temperature and Partial Pressure Dependences of Partial Conductiv

ities
In the previous section we saw the key roles played by the
various partial conductivitiesor equivalently the transference
numbersin mixed conduction theory. They appear prominently in
the integrands of the formulas for open circuit emf and scaling
rate. Thus, i f they exhibit any dependences on partial pressure
p ~ which is equivalent to u ~, these dependences w i l l have very
x

106
direct effects on the scaling rate and emf values predicted by

the theory. In this section a useful scheme for visualizing these
dependences is provided.
To begin with we note that the crucial thing here is the de
pendences of the various p a r t i a l conductivities on temperature and
If these could be determined reliably from direct experimental
measurements, a l l the important predictions could be made by merely
using those dependences in the integral formulas derived previously.
In this sense the defect theory and mass action laws which are used
to rationalize the dependences would be of only secondary importance.
However, i t is not expdient to rely on measurements only in
cases like this because too many would be required. Thus, the
theory of defects provides a number of rather general laws concerning the dependences of interest so that far fewer measurements are
necessary for us to arrive at many meaningful predictions and useful extrapolations.
Very b r i e f l y the conductivitie
compounds can be writte
2
2 2
. = c.V. q./kT
20
where c i is concentration,
is
jump frequency, is temperature
and everything else is constant (jump distance 1, Boltzmann's k
and charge q^) . Thus, the temperature and P
dependences of the
conductivities are due to those of c i and Vj_. In general Vj[ w i l l
always exhibit an Arrhenius dependence on temperature because
hopping is a thermally activated process. This means
will a l
ways go as exp
(-Q/RT) where Q is a constant called the a c t i
vation energy. No dependence of
on partial pressure is ex
pected theoretically and none are found experimentally.
The concentration term has a b i t more f l e x i b i l i t y for d i f f e
rent behaviors: two kinds of temperature dependences (constant or
exponential) and two kinds of p a r t i a l pressure dependences (con
stant or exponential). Beginning with the temperature dependence,
c i w i l l either be independent of temperature or i t w i l l also ex
hibit an Arrhenius dependence, albeit with a different activation
energy than that exhibited by V i . If the carrier concentration is
fixed by extrinsic contaminations, deliberate or not, i t w i l l re
main independent of 2 In some cases however, the concentration
may be small enough that incorporation of atoms from the ambient
2 w i l l cause changes. On the basis of the law of mass-action
arguments, etc., these c i generally vary as Here,
is a constant, usually a ratio of small integers, which ratio is
characteristic of the defect reaction whose equilibrium is in
volved.
The result of a l l of this is that when individual conducti
vities are plotted on a log scale versus log and reciprocal
absolute temperature 1/T, planar sheets generally always result.
This means that only a few measurements (3 minimum) are needed to
x2

PATTERSON
4.
Conduction
in
Nonmetallic
Phases
107
estimate values at other conditions. Figure 4 shows an example of

the kinds of dependences that can occur. Note that the various
conductivities plot as planar sheets though they are tipped at v a r i
ous angles.
Actually, the dependences portrayed in Figure 4 are
typical of those found in solid electrolyte materials. The log
and log
sheets are seen to rise up from far beneath the
independent ionic conductivity sheet. Thus, they dominate the to
t a l conductivity in the very high and very low Px regimes. This
means that t - ^ =[+2]/ must f a l l o f f to zero in these extreme
conditions. By considering any particular isotherm of such a threedimensional plot, we can generate any plot of [ t + t ] / 2 Z F vs
that he may need: as for example to evaluate an open c i r c u i t emf
in accordance with Equation 11 above. Alternately, he could generate
a plot of 03 [ t + t ] / 2 Z F vs i f a prediction of scaling rate
from Equation 19 was desired.
A more expedient approach would
be to simply write the dependence int compute
which
then carry out the desire
on
Capstone Comments on the Open Circuit Theory of Parabolic Oxidation

We have looked at many aspects of the traditional theory of
mixed conduction, but many stones have been l e f t unturned. There
are implications for the morphology of scaling layers, why they
are so uniform in thickness and why one cannot retain that mor
phology i f he t r i e s to buck the scale emf in an attempt to make
i t grow thinner. There are many interesting predictions that can
be made and tested concerning the morphology of the reaction inter
face formed when a metallic oxygen "getter" is put in contact with
(and hence reduces) the oxide of a more noble metal. Sometimes
the interface morphology is planar, sometimes not; however, the
c r i t e r i a for determining this stem mainly from Wagner's theory.
There are the many open c i r c u i t emf studies that have been
carried out to search for new solid electrolyte materials. The
specimen is placed in contact with electrodes which establish
Il
I
different but known partial pressures P , P
and the emf is
measured. The ratio of the measured emf to the thermodynamic
voltage calculated from Equation 7 gives a quick estimate of
the materials ionic transference number, as implied by Equation 6
above. This is an estimate to be sure, because the ratio actually
averages the value of t^
over the scale. But the method very
quickly reveals which materials might best be ruled out for fur
ther studies. Indeed, those which persist in registering a zero
measured emf are predominantly electronic conductors and probably
not much can be done (e.g., by way of doping etc.) to make them
into ionic conductors, i.e., solid electrolytes.
There is also the matter of predicting the high temperature
gas permeability of ceramic tubes. When an M X^ compound is^pro
perly affixed to i t s metal M as a scale, the calculation on
from Equation 19 can be translated into weight gain-or scale thickx2
x 2
on

108
journal or tne tiectrocnemicai society

Figure 4.
Schematic of the F , dependence of partial and total conductivities

(40)
x2

4.
PATTERSON
Conduction
in
Nonmetailic
Phases
109
ening kinetics. But, i f i tis.not in contact with i t s own metal,

i t cannot thicken and then n is simply i t s permeability to X 2
gas. For example, a sintered, crack-free oxide tube w i l l leak
oxygen from an oxide i f i t is evacuated at high temperature at a
rate governed by the assimilation rate into the outside surface of
the tube and subsequent oxide ion migration through this wall.
Thus, Wagner's theory can be used to predict how much oxygen w i l l
permeate the tube in any given time. If the tube material is pre
dominantly an electronic conductor, this permeability becomes a
measure of the chemical d i f f u s i v i t y for oxygen in the compound.
However, i f i t is a solid electrolyte material, e.g., doped zirconia
or thoria, the permeability is limited by electronic conduction.
Thus, some of the best estimates of positive hole conductivity in
the oxide solid electrolytes have come from "gas permeability"
studies made on tubes of these materials.
Actually, the l i s t
and certainly many have
wanted to provide a brief introduction to Wagner's ideas and perhaps
some appreciation of the underlying fundamentals.
We w i l l now be turning to the second part of this paper in
which Wagner's ideas w i l l be extended to nonopen c i r c u i t conditions
and somewhat more general kinds of mixed conductors. Before doing
that, however, l e t us close off Part I here by drawing attention to
the spectacular agreement between measured and calculated sealing
rate constants that stirred up so much in the f i r s t place. Thus,
we close Part I with the summary Table I which is adapted from one
given by Kubaschowski and Hopkins ^^ The close agreement shown
in the two right-most columns seems a l l the more outstanding when
the absolute magnitudes are considered.
x
T a b l e I . C a l c u l a t e d and Measured
Rare C o n s t a n t s f o r t h e F o r m a t i o n
of M e t a l - Ncn M e t a l Compounds
NON-METAL
COMPOUND
TC
( r e f . 26, 77)
"RATIONAL RATE CONSTANT"
EQUIVALENT x cm" sec ""
1
Calculated
Ag
(liqj
Ag S
2
220
2.A 1 0 "
Observed
1.6 1 0 "
1 0
61
x^lO"
1 0
3.8 1 0 "
1 1
Cul
195
3.8 X "
AgBr
200
2.7 X 1 0
Cu 0
1000
6.6 X
6.2 1 0 "
Cu 0
1000
4.5 1 0 "
Cu
o;
- 2.3 X 10" atm.
Cu 0
1000
4.8 X 1 0 "
_q
3.4 X 10
Cu
2
a tin.
atm.
0 ; - 1.6 X 10"
0 ;
- 3.0 X 10" atm.
Cu 0
1000
2.1 X 1 0 "
Cu
2.2 1 0 "
Cu
Ag
Br
Cu
(Ss)
(gas)
0 ; - 8.3 X 10"
2
- 1 1
3.4
"
9
.9
3.1 x 10

110
Part II Multicomponent Mixed Conductors Under Closed Circuit Conditions

Motivating Factors
In part I above, c. Wagner's theory of mixed conduction
was reviewed in terms of an equivalent c i r c u i t approach. The implications of mixed conduction theory for parabolic scaling of
metals in high temperature atmospheres were also detailed. It was
pointed out, however, that current interest in mixed conduction
theory is no longer motivated by corrosion considerations; because
far too few systems of practical interest conform to the conditions
required for parabolic oxidation.
Instead modern interest in mixed conduction theory is expected
to derive from high temperature solid electrolyte applications.
These solid electrolyte
Wagner's theory and man
which would require devices based on such solid electrolytes. Some
of these applications are of the open c i r c u i t variety such as solid
electrolyte emf sensors for high temperature environments where
contamination of the electrolyte may be a problem. But many other
applications w i l l be of the closed c i r c u i t variety and to a large
extent this aspect has not been negotiated very rigorously in the
traditional theory. Significant extensions of the traditional theory
w i l l have to be made before the performance characteristics of fuel
cells and high temperature steam hydrolyzers can be successfully
analyzed via the theory of mixed conduction in solids.
Moreover, hydrogen w i l l l i k e l y be present in many of these applications and i t is known that hydrogen dissolves into oxide solid
electrolytes and becomes a mobile charge carrier. Thus, in addition
to extending the theory to close circuit or load conditions, i t is
also desirable to extend i t so that the effects of mobile foreign
ions such as hydrogen can be treated ( 2 7 - 2 9 ) .
Here in Part II,I w i l l conjecture about how to extend
Wagner's theory in these important ways. Thus, we shall examine a
situation in which an understanding of electrochemical corrosion
is being used to launch into other areas of interest which at f i r s t
blush might seem t o t a l l y unrelated.
What is clearly needed is a working model for multicomponent,
mixed-conducting electrolytes, one which would be applicable to
closed as well as open c i r c u i t conditons and yet would be relatively

4.
PATTERSON
Conduction
in
Nonmetallic
111
Phases
easy to understand intuitively. Thus, an improved dc c i r c u i t

analog seems to be called for and one is developed below which
serves the purpose. It is an extension of the one described by
Choudhury and Patterson(19,24) which in turn, is very similar to
that suggested long ago by Hoar and Price(25; j their "electrochemical interpretation" of Wagner's theory of parabolic scaling
( 9 ) and to that of Mi ley (30) who interpreted other scaling rate
laws from the equivalent c i r c u i t viewpoint. More recent discussions of these kinds of c i r c u i t analogs can also be found (31,32).
The present paper furthers the discussion of these kinds"of
c i r c u i t models in two major respects. The f i r s t has to do with
the point-to-point variations which may be expected to occur. This
has been discussed to some extent by Choudhury and Patterson (19, 24).
They provide a very useful parametric method which automatically
adjusts the local resistances but i t was not presented in a form
that is easy to visualize
w i l l be outlined here whic
traditionally accepted "fixed resistor analogs. The second major
point has to do with extending the equivalent c i r c u i t models in such
a way as to allow for additional mobile ionic species in the electrolyte .
The mixed conducting medium considered here is generalized in
the sense that the number of mobile ionic species is l e f t open; but
the treatment is specialized in that steady state conditons are
presumed. A more rigorous treatment of a s t i l l more generalized
medium has been given by Wagner (33), but i t seems to be restricted
to open circuit cells only.
In the present treatment, both charging and discharging modes
are considered in addition to open c i r c u i t operation; however,
only diffusive transport is permitted in the electrolyteconvection is not. Consequently, the results are most directly applicable to solid electrolyte media; however, l i q u i d media (acqueous,
molten salt, etc.) in a previous matrix should also conform to
such assumptions.
By and large, phenomena extraneous to the electrolyte, such
as electrode exchange kinetics and the l i k e , have been deliberately
separated out of the present treatment by assuming that a l l pertinent chemical potentials are given at the electrode boundaries.
Concentration polarization effects at the electrode surfaces could
be accommodated here by invoking models which simulate the electrode kinetic phenomena. These would relate the chemical potent i a l s out in the electrode to the ones just inside the electrolyte
(which are presumed here to be given). Interfacial differences in
chemical potential would thus be brought into the present analysis
in much the same way that voltage drops at contacts are brought in
as I R drops in regular c i r c u i t theory. However, since electrode
models are not within the intended scope here, the endpoint or
i n t e r f a c i a l drops w i l l not be given e x p l i c i t consideration below.
n

112
CORROSION
CHEMISTRY
Transport in a mixed conducting medium is treated here,

but only in terms of ion and electron migration. This avoids
unnecessary confusions in connection with defect theory and em
phasizes the fact that important results can be arrived at quite
independently of specific assumptions about the defects involved
(19) . Any further breakdown of the ions and electrons into defect
species is neither necessary nor desirable for most purposes.
This is accepted for liquid electrolytes (33), but i t may seem sur
p r i s i n g that the use of ionic and electronic imperfections (34) can
be avoided when treating solid media; indeed, defects are undoubtedly
responsible for transport in s o l i d electrolytes . By resisting
this temptation, however,(as Wagner did originally) we actually
arrive at formulas of a more general nature which can be special
ized l a t e r in accordance with whatever defect structure may seem
most appropriate.
Fundamental Consideration
Consider a generalized, mixed-conducting electrolyte inter
posed between two electrodes as shown in the c e l l configuration of
Figure 5 .
The term "mixed conductor" is used here to indicate
that electron transport is not ruled out.
The electrochemical potentials of the k different ionic species
are represented as n^, i = l , 2 , 3 , . . . k , while the chemical potentials
of the corresponding neutral species are denoted by y i , or perhaps
( 1 / 2 ) \i2
*- l / 2 , . . . k . For example, i f species 1 were zirconium,
might refer to Z r ^ cations, whereas ^ would be the molar Gibbs
free energy of uncharged or neutral Zr metal. However, i f one of
the other species, say species 2 , were oxygen, then the electro
chemical 'potential symbol 2 would be replaced by T)Q-2 to denote
the molar Gibbs energy of the oxide ions 0 " " 2 . But in this case
1 / 2 P 0 2 l d be used for the neutral species because neutral
oxygen ordinarily exists in the form of dimeric gas molecules.
A similar approach would be used for N , 0 1 2 , B r , F , etc. The
electrochemical potential for electronswhich have no neutral
counterpartis denoted by n .
Since the species in an electrolyte are charged, electrochem
i c a l potentials
and p a r t i a l conductivities O i (which r e f l e c t
the species mobility) are both used in Figure 5 .
Conditions at the
l e f t electrode surface = 0 are indicated by a single prime while
double primes signify those at the other end, = L.
Traditionally, the chemical potential ^ characterizes only
the chemical energy interactions between a species i and i t s sur
roundings. If a charged species is involved, interactions of an
electrostatic nature must also be considered. Accordingly, the so
called electrochemical potential is conceived in such a way as
to include both types of energy as follows
=
w o u
. = . i + Z.F<j>
1 1

21
4.
PATTERSON
Conduction
in
Nonmetallic
Phases
113
Here y represents a l l the chemical interactions between the ion

of type i i t s surroundings and Z^F represents the electrostatic
part of the electrochemical potential. Thus, Z^ is the valence of
the ion, F is the Faraday, and is the local electrostatic po
tential. Actually, the separation of chemical and electrostatic
components in this way is based more on conceptual preference
than on operational meaningfulness (35, 36). but the separation has
a great deal of h i s t o r i c a l precedence and is mentioned here for
that reason. But the approach used here does not make use of
such distinctions and in this sense at least would be in accor
dance with the recommendations elaborated by Guggenheim (35) . i t
may be called the local equilibrium approach and may be summarized
as follows.
The electrochemical condition at each point in the medium
i.e., the concentrations and mobilities of i t s constituent ions
and e l e c t r o n s i s determined b th prevailin chemical potential
or a c t i v i t i e s of the constituen
cordingly, point-to-point variations in the medium are most meaning
fully characterized either in terms of voltage profiles or in terms
of chemical potential (activity) profiles of the appropriate neu
t r a l species or in terms of both. That is, only voltages (electric
potential differences operating on ions and electrons) and che
mical potential differences for neutral species (not those for
the ions) are amenable to direct measurement and control(19,35,36).
Thus, even though the electrochemical potential profiles and gra
dients for ions and electrons arise quite naturally from the basic
flux equations given later, they are to be eliminated in favor of
their more measurable counterparts. This elimination process is
effected by assuming local equilibrium for internal dissocation re
actions and proceeds along the following lines.
If Z-L is the valence of ionic species i in the medium, the i type ions and electrons may be related to the appropriate neutral
species, but equilibrium of the following dissociation reaction
must be presumed
.
i
(or h. )*i
2
+ Z^
22
Formally, this prototype reaction serves for cations as well as

anions. Cations by definition always have positive values and
derive from metal atoms. As an example of this, the following
reaction, which would apply to the zirconium constituent in the
well known solid electrolyte calcia-stabilized zirconia (CSZ),
may be cited
Z r Zr
+ 4e
^3
Anions, on the other hand, always have negative values; hence

Equation 22 applied to the oxygen ion constituent of CSZ yields
(1/2)0
0~ - 2e. However, transposing the -2e yields the more
2

114
familiar form
0
+ 2e-* 0
24
By assuming local equilibrium of the dissociation reactions,

a zero free energy condition results which relates the l o c a l che
mical potential of the neutral species to the charged species ac
tually present. Thus, local equilibrium of re act ion (22.) implies
the following generalized free energy equality
u. =
IT.
25
Z.n
Note that Equation 25 embraces as special cases the zirconium

oxygen examples mentioned e a r l i e r . In particular we have
and
26
and
Thus the single relation, Equation 25, can indeed be used to

eliminate electrochemical potential differences for both cations
and anions. One is then l e f t with chemical potential differences
for neutral species (which are measurable) and electrochemical po
tential differences for electrons which are directly related to
measurable voltages Vj_, as follows (19.24.37.38)
" - ' = Z FV = FV
e
e
e L
L
28
where Z is -1 and, again, F is the Faraday. Certain precautions

are necessary, however, because the leads to the measuring device
must be good electronic conductors and must be identical in che
mical composition (35,37,38). identical composition is also re
quired to avoid the thermocouple emf s that can arise when the c e l l
and measuring instruments are at different temperatures.
By combining Equations 25 and 28, the electrochemical potential
i ~ i f i y P ions may be written in the following abbreviated
form
e
- t
'.' - ! = -Z.F[V. - v j
i l
29
where for convenience, the abbreviated symbol Vi has been substi

tuted to save writing out the chemical potential differences for
the corresponding neutral atoms. For monoatomic species, the sub
stitutional r e l a t i o n employed is
V. =-[ V
- y!] /Z.F

30
PATTERSON
4.
Conduction
in
Nonmetallic
115
Phases
but again i f the neutral species is ordinarily a dimer gas such as

0, Cl
etc., then is given by
2
31
The quantity is of fundamental importance and w i l l be referred
to hereafter as the thermodynamic voltage for species i i t re
presents the chemical driving force or a f f i n i t y which acts to
drive the i-type ions through the medium. Like V ,
has units
of volts.
It is worth digressing here to point out some important points.
F i r s t of a l l i t should be noted that differences or gradients in
are a measure of the overall or combined "driving force" for
migration of the i type p a r t i c l e s . However, in view of Equation 29,
we see that this overall "force" has two parts: A chemical gra
dient part arising from
nent arising from difference
cases of practical interest these two parts oppose each other and
the direction of net migration is determined by whichever is the
stronger force. In electrolysis (charging mode) the V L gradient
is stronger whereas in the discharge mode the chemical driving
forces prevail. And for multicomponent electrolytes i t is most
important to realize that some species may be undergoing electro
l y s i s while others are simultaneously discharging in the same cell.'
This possibility has profound implications for the performance
characteristics and efficiencies of practical electrochemical de
vices of a l l types.
L
If the c e l l electrodes have a v i r t u a l l y i n f i n i t e capacity,

the endpoint values of ^ w i l l not d r i f t towards each other to
any significant extent even under constant load when ionic per- meation is taking place through the electrolyte. To simulate this
condition is thought of as a fixed quantity as i f i t were a
battery voltage. For example, coexistence metal, metal oxide elec
trodes in an oxide solid electroltye c e l l , would function in this
way.
However, i f the electrode chambers are of very limited ca
pacity, the endpoint chemical potentials w i l l vary as ions pass
through the electrolyte. The "thermodynamic voltage"
changes
accordingly and in this sense V i acts more like a capacitor than
a battery. In such cases, we might wish to show a capacitor in
the equivalent c i r c u i t to emphasize the variable nature of V
when
V overpowers V i , i ions are forced backwards; that is, from the
low to the high chemical potential sides and V-^ builds up in value
much as i f i t were a real capacitor being charged by a battery.
And of course when V i overpowers V , ions flow from the high
chemical potential side to the low and
drops as the electrode
inventories approach each other.
In contrast to the ionic species, the thermodynamic voltage
for electrons always remains at zero. Their state of charge is
2
i#

116
not altered by merely passing through an electrolyte/electrode

interface and also unlike the ions, there is no neutral counterpart
to an electron. This is taken into account by always setting V
to zero in any electronic branch of an equivalent c i r c u i t .
e
Steady State Migration Fluxes in Multicomponent Electrolytes and

the Central Problem with Closed Circuit Theory
The flux of charged species i past any point in an electro

l y t i c medium is taken to be proportional to the magnitude of the
prevailing electrochemical potential gradient Vn^, with flow d i
rected down that gradient. However, i t is more useful in the pre
sent approach to work with the e l e c t r i c a l current due to species
i . This current 1^ is internal to the electrolyte and thus can
not be measured separately; but the following formula for
can
be inferred from the diffusio
I. = -A ^- Vn. = -A
[VV. - W 1
32
l
2.F
x
Z. F
Here, A is the cross-sectional area perpendicular to the flow d i

rection, F is the Faraday, and
is
the specific e l e c t r i c a l con
ductivity (in the appropriate units) for the charged species in
question. Writing the constant of proportionality in terms of
is somewhat arbitrary, but i t is certainly not without precedent
(19,24). Nevertheless, i t is worth noting that the absolute mobi
l i t y , the e l e c t r i c mobility, the d i f f u s i v i t y or the transference
number-total conductivity product may replace -[ as the transport
parameter of central interest, and such alternatives are sometimes
used.
After steady state sets in, Equation 32 becomes constant be
cause I j.the current carried by each species imust be invariant
from point to point along the direction of flow. Then the follow
ing operations are carried out to get the important result of Equa
tion 33 below: Equation 32 is f i r s t solved for Vn^, then i t is
integrated from to L to get - n| in terms of 1^. Next Equa
tion 29 is used to eliminate ? and the result is solved for
the constant I^. The f i n a l result of a l l this is
J
I. = G.[V. - V 1
x
i
l
L
33
where G^ here is simply the reciprocal of R^ which in turn is the

total series resistance presented by the c e l l to species i . Thus
Gi is the macroscopic conductance for species i according to the
formula
L
G. =
*
I - !
34
LJ 0
() A(x) J
i
1
rf

4.
PATTERSON
Conduction
in
Nonmetallic
117
Phases
Since planar geometry is assumed here, A(x) may be replaced by a

constant; however, other geometries could be considered by merely
employing the appropriate A(x) dependence.
Of course the dependence of
on is also required i f the
integral in Equation 34 is to be evaluated. But determining that
dependence is such a complicated matter that no solution can be
given here at least for the most general case. For this reason,
this matter of evaluating the conductance term
defined in
Equation 34 is the single most d i f f i c u l t problem here and i t a l
ways arises when one t r i e s to extend the theory of mixed conduc
tion to non-open c i r c u i t conditions. In particular we must not
only know how
depends on the chemical potential of i or p a r t i a l
pressure or activity but in addition he must also determine the
chemical potential p r o f i l e . But even worse than that, this pro
f i l e w i l l in general vary depending on the load conditions. This
introduces a troblesome non-linearity into the theory because we
cannot rule out the p o s s i b i l i t
tage or current dependent
solved only in special situations where the conductivity properties
of the solid electrolyte are presumed to be known functions of
temperature and p a r t i a l pressure P It may be helpful at this point to explain why the formidable
"central problem" discussed above doesn't show up in the t r a d i
tional theory of mixed conduction as developed by Wagner. He
only treats two situations: ion blocking electrode conditons and
open c i r c u i t conditions. When the electrodes are ion blocking, I i
vanishes in Equation .32 (for each ionic species) in which case
Equation 32 is easy to integrate.
In open c i r c u i t situations, the sum of a l l the I s vanishes
and, though the integration is not quite as simple as for the ion
blocking case, s t i l l a closed form integral relation can be de
rived which holds for a wide variety of solid mixed conductors.
In fact the formula that results in this way is Wagner's well known
open c i r c u i t emf formula (Equation 31 in part one) and applies to
any binary (two component) mixed conducting compound.
Returning to the main thread here, we note that Equations 33
and 34 apply to each mobile species individually; however, in a l l
cases of practical interest simultaneous migration of more than
one species must be considered.
This is especially true in the
case of multicomponent electrolytes in which many kinds of ions
may be mobile. But i f several species are in motion they merely
make simultaneous contributions to the current exchanged with the
external c i r c u i t . The relative contribution of each w i l l depend
on the ease of transport in the elctrolyte, i.e., on G^ and on the
chemical and e l e c t r i c a l potential gradients which act on i t .
But
these matters are better discussed in terms of the extended equi
valent c i r c u i t approach which w i l l now be developed.
x2

118
Equivalent Circuit Relations
It is f r u i t f u l to reconsider a l l the foregoing notions in

conjunction with the simple dc c i r c u i t analog shown in Figure 6.
The k parallel branches in the c i r c u i t model automatically account
for the simulataneous contributions made by a l l the ion species to
the external (load) current I . To minimize confusion, a l l cur
rents (including IjJ are considered positive i f they are directed
to the right in the c e l l , and V as well as any thermodynamic v o l
tage is positive i f i t s positive terminal is to the right (toward
= L) in Figure 6. Confusion about the direction of species mi
gration in relation to the sign of i t s charge can be greatly re
duced by focusing only on the currents (rather than the diffusion
fluxes) because the signs and directions of currents and voltages
are easier to think out. Some would say the conventions make i t
a l l automatic.
According to Kirchhoff'
obtained by summing over a l l the p a r a l l e l branches
k, e
I = I + I- + . .. I. + I = I.
35
L
1
2
k
e
k,e
where indicates that the summation on i goes from 1 through k
(all ion species) with a f i n a l term for the electron contribution
as well. This symbol is used below as well.
If we insert Equation 33 for each I^ in Equation 35, collects
terms, and then notes that the same load voltage
whatever that
turns out to b e i s necessarily impressed on each of the parallel
branches, we can produce the following sequence
k,e
k,e
k,e
L
= Z
G [V.-V ]=S
I
= s
G.V.-V^
3 6
'Vi-V
where
the k,e notation means the same as i t did above. Also, to
simplify notation here, the total conductance G and the transference numbers t ^ have been introduced. They are defined as
follows :
k,e
G
Q ~
G.l
37
T
and
t. = G. / G .
38
T
however the G^ values in 37 and 38 derive from the troublesome
Equation 34.
The transference number t ^ may be regarded as a kind
of normalized conductance or conductivity. These definitions to
gether with Equation 36 yield
=T ^- L

39
4.
PATTERSON
Conduction in Nonmetallic
Phases
119
-,(), ^ )
LEFT
: ^
ELECTRODE ^
: RIGHT
' ELECTRODE
MEDIUM
n (x), a (x)
k
n (x). ( )
e
I-
= 0
Figure 5.
Schematic of a generalized electrochemical cell
1/R1
CELL
ANALOG
-AW-vw-wv-
EXTERNAL
LOAD
CIRCUIT
LOAD
RESISTOR
Figure 6. Direct current (dc) analog for a multicomponent mixed conducting
electrolytic cell

120
where V is also a shorthand symbol.

_
k
V = t V.
I t stands for the summation

40
and is a quantity of considerable significance. Equation 40 should

also include a term t V but this has been deleted here because
V is always zero.
V represents the overall thermodynamic driving force for the
c e l l and is seen to be a weighted average of a l l the individual
thermodynamic voltages V^. The weight factors are the transfer
ence numbers t ^ which means that each V-^ has been weighted in
proportion to the conductance
with the result normalized to
the total conductance of the electrolyte. To evaluate V, the
V^'s are f i r s t calculated from Equation 30 or 31. and then each
is multiplied by the corresponding transference number in order
to form the normalized weighte
cal interpretation for V
those familiar with ternary phase diagrams, is presented in Fig
ure 7.
With Equations 34 and 37-40, v i r t u a l l y a l l the essential pro
perties of the electrolyte have been brought into the analysis.
However, the external c i r c u i t t h e agent for exchanging charge
and energy with the cellmust also be brought in i f meaningful,
performance analyses are to result.
In order to examine the performance characteristics of a c e l l
under load, we l e t the external c i r c u i t consist of a variable ohmic
resistor Rj, whose value may range anywhere from zero to i n f i n i t y .
In this sense, the load conductance G may be regarded as a con
venient control parameter which permits various current-voltage
load conditons to be placed on the c e l l at w i l l . Ohms law for
the external element yields
e
which together with Equations 39 and 40 completes the basic system

of equations needed for the present analysis.
For most performance analyses, however, i t is better i f ex
p l i c i t formulas for V , I , and the power W = I V are available.
That is readily accomplished as follows: f i r s t one solves Equa
tions 39 and 41 simultaneously for V and I and then multiplies
the two to give W.
This results in the following three equations
which are parametric in G :
G_
L

4.
PATTERSON
Conduction
in
Nonmetallic
Phases

121
122
- 2
44
Equations 37-44 with Equations 30 and 31 serve as a system of
basic relationships that are quite useful for analyzing the performance of a generalized electrochemical c e l l under various modes
of operation.
It is worth re-emphasizing, however, that the mathematical
simplicity of the equations in this system may be simplicity in
appearance only. Again, the
quantities in G and in the various t-L values which enter into V are not necessarily constant
in general: rather, they are apt to vary somewhat with loading
conditons as was pointed out in the discussion subsequent to Equation 34 above.
T
Capstone Comments
This is one of those tasks that one never really finishes.
Rather one pauses from time to time to sum up, hoping either to
continue again later or perhaps to abandon the effort for good.
In this case I hope to continue, at least for a while, and in
summing up here, l e t me explain why I w i l l only use one example
to do this but many others exist as well.
There have been cases wherein a fluoride ion solid electrolyte,
in particular CaF , has been placed between two different metal
oxide electrodes and behaved as i f i t were an oxide solid electrolyte. That is, the emf was found to be equal to that measured previous with calcia- or y t t r i a - s t a b i l i z e d zirconia! No very suitable explanation has been offered yet, but I think that these
findings have been published or soon w i l l be. But i f my conjectures above are correct, the following explanation could be offered.
The CaF electrolyte is capable of incorporating oxide ions
and transporting them simultaneously with, but perhaps to a much
lesser extent than, fluoride ions. Then CaF could be thought of
as a two-anion electrolyte. Since the electrodes are reversible
and highly "buffered",as i t were, with respect to oxygen, the
thermodynamic voltage V for oxygen acts like a stable battery
in the equivalent c i r c u i t . There is of course a fluoride ion
branch as well, but i t s thermodynamic voltage V behaves not like
a stable battery but rather like a capacitor. This is due to the
fact that fluorine inventories are not fixed by the oxide electrodes and so the trace amounts that do reside therein can change
drastically as the fluoride "counter-ions" get pushed in the d i rection opposite to the flow of oxide ions through the CaF ". In
short, the battery-like voltage V in the oxide-ion branch of the
2

4.
PATTERSON
Conduction
in
Nonmetallic
123
Phases
c i r c u i t charges up the capacitor-like thermodynamic voltage in the

fluoride branch until they become equal. At this time, the load
on V drops off considerably since i t then has only to "back-pump"
the trace amounts of electrons that leak through the CaF (the e
branch). If electronic conduction is small, as in tbe case here,
the steady state c e l l emf w i l l v i r t u a l l y equal V a s observed!
As I said this is only one example though many others could
have been given. I am presently trying to outline similar explanations for other confusing d r i f t effects in s o l i d and molten
electrolyte devices. It simply is not appropriate here to l i s t
the p o s s i b i l i t i e s ; however, I w i l l say that some of the most
fascinating and important
(but alas! most complicated and d i f f i c u l t ) applications may be found in the area of fuel c e l l s and
batteries. And many of these devices are based on multi-component
electrolytes.
I only hope that mor
in solving the central
above, namely, that of evaluating the individual ionic conductances
and chemical potential p r o f i l e in an operating c e l l . And of course
I hope I can be a p a r t i a l contributer to such future progress. Or
better yet, that somebody in the audience w i l l be led to contemplate
the issues I have discussed here and perhaps find a better way to
analyze mixed conduction in multicomponent electrolytes.
Q
Acknowlegement
Preparation of this manuscript spanned many months but i t
had to be put into f i n a l form during o f f hours while I was on a
summer leave of absence from ISU. I was working in Dr. Hugh
Isaacs group at Brookhaven National Laboratory at the time and
I am indebted to many of the BNL people for very helpful discussions.
Of utmost importance at that time was the willingness of
Ms. Yvonne Oden to sacrifice many of her off work hours, thus
making i t possible to complete the manuscript just before the
deadline. I shall be forever in her debt for that.
I also wish to acknowledge the Iowa State University, Engineering Research Institute for continued financial support of
research in high temperature electrochemistry and for help
during the i n i t i a l stages of manuscript preparation.
Finally, I wish to thank the Chicago Chapter of the Electrochemical Society and my host, Prof. Bruce Wagner for their kind
invitation and cordial hospitality.

124
CORROSION
CHEMISTRY
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4.
PATTERSON
Conduction
in
Nonmetallic
125
Phases
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K. Denbigh, Principles of Chemical Equilibrium, Cambridge

Univ. Press, Cambridge, U.K. (1968), section 2.9
J.W. Patterson, Ind. Eng. Prod. Res. Dev. 17(1), 19(1978).
J.W. Patterson, J. Electrochem. Soc. 118(7), 1036 (1971).
39.
40.
RECEIVED
September 1, 1978.

1540
5
Dissolution of Iron
MORRIS C O H E N
National Research Council of Canada, Division of Chemistry, Ottawa, Canada
In this lecture I w i l l deal with the mechanisms involved in

first,
the dissolution or corrosion of iron and second, in the
inhibition of corrosio
oxide films. A few definition
the specific nature of my subject.
Mechanism
1. A sequence of steps in a chemical reaction.
2. The fundamental physical processes involved in or responsible for a reaction.
Dissolution
The act or process of dissolving or breaking up.
Corrosion
Destruction of a metal by chemical or electrochemical reaction with i t s environment.
Inhibitor
A chemical substance which, when added to the environment,
usually in small concentrations effectively decreases corrosion,
after concentrations.
Passivity
A metal is passive if it substantially resists corrosion in
an environment where thermodynamically there is a large free
energy decrease associated with i t s passage from the metallic
state to appropriate corrosion products.
Corrosion and i t s inhibition or passivity both involve reactions between the metal surface and the solution. In the case
0-8412-0471-3/79/47-089-126$06.75/0
1979 A m e r i c a n C h e m i c a l Society

5.
COHEN
Dissolution
of
Iron
127
of corrosion the reaction products are either soluble or form

solids which are either loose or porous and do not protect the
metal. In the f i r s t part of this presentation I w i l l deal with
conditions in which corrosion of iron continues while in the last
part I w i l l outline some of the mechanisms for the formation of
solid protective films which can lead to both anodic passivity
and inhibition.
Surface of Metal
Metals normally exist as polycrystalline solids in which the
atoms are arranged in a manner characteristic of the metal. The
atoms in iron are arranged in a cubic array, (i.e.) the metal is
composed of groups of cubic cells in which there are iron atoms
at each corner of the cube and one in the middle. Large groups
of these form crystals which join with some misfit at grain
boundaries to make up th
grain boundaries other
boundaries, dislocations, vacancies and either segregated or
soluble impurities. Of course, a l l of these imperfections show
up at the surface and affect the manner in which the iron w i l l
react. Some of these imperfections are shown in Figure 1 . In
this figure one can see ledges, impurity atoms, vacancies where
an atom is missing and a kink step which results from the emergence at the surface of a dislocation. These imperfections w i l l
a l l have different reactivities and at near equilibrium conditions, w i l l react at quite different rates. Under conditions
far from equilibrium, such as in electropolishing the imperfections w i l l have very l i t t l e influence on dissolution rate and
smoothing takes place. Under etching conditions both the effects
of imperfections and crystal structure can be observed. This is
shown in Figure 2 for iron electrolytically dissolved in perchloric-acetic acid in the etching region. On different grains
one can observe either triangular or tetragonal pits, depending
on the orientation of the grain.
Aside from basic structural imperfections the dissolution
rate and mechanism can be markedly affected by both bulk and surface impurities. Some surface impurities may act as preferred
sites for hydrogen atom recombination and hydrogen evolution and
hence increase the rate of dissolution. Others may act to poison
the hydrogen re-combination reaction and lead to hydrogen dissolution followed by embrittlement and cracking. Some bulk impurities act as nucleating points for hydrogen atom recombination and lead to blistering. Carbon in iron is a hardener and
makes iron more susceptible to stress-corrosion cracking. These
effects make i t necessary to study both the surface and bulk
composition of the iron in order to predict i t s corrosion behavior .

128
Figure 1.
Imperfections on solid sur

faces
Figure 2.
Geometric pitting and grain boundary etching in anodic dissolution,

original mag. 30,000

5.
COHEN
Dissolution
of
129
Iron
Solution Composition
The second reactant in the dissolution or corrosion system
is the solution. In most cases this is basically water contain
ing dissolved substances which ionize more or less to cations and
anions. The solution may also contain dissolved gases such as
2> H , or C0 .
These constituents of the aqueous system can
affect the corrosion rate in a variety of ways. 0 in small
amounts may act to increase the rate of corrosion and in s u f f i
ciently high concentrations to inhibit i t . In the presence of
chloride ions, pits tend to go acid with a consequent increased
rate of dissolution of the iron. Some metal ions such as copper,
plate out on the iron surface by an exchange reaction and increase
the corrosion rate by acting as hydrogen depolarizers.
Complexing agents increase the reaction by lowering the effective
concentration of the dissolved ferrous ions. Other constituents,
such as organic amines
the rate of solution. Others
or molybdate, help to form protective oxide films and inhibit the
dissolution reaction. Hence a knowledge of the effects of
various possible constituents of solutions is necessary before
predicting the corrosion behavior of iron.
2
Application of Thermodynamics
With sufficient thermodynamic and equilibrium data i t is
possible to predict whether or not a dissolution reaction w i l l
take place. Also with a knowledge of the free energy change
for a reaction one can calculate the potential at which the
reaction w i l l occur from the relationships
AG = nFE
and = E
nF
+ log Concentration
where AG is the free energy change for the reaction, is the

number of electrons involved, F is the Faraday and E is the Stan
dard Potential.
Using these considerations, M. Pourbaix and co-workers at
CEBELCOR constructed "equilibrium" potential-pH diagrams showing
some of the stable phases for iron in aqueous solutions.Q)
By
further assuming that the formation of a stable solid oxide would
lead to s t i f l i n g of corrosion (passivity), he simplified the dia
gram for iron to that shown in Fig. 3. In this diagram areas of
pH and potential are designated by the terms Immunity, Corrosion
and Passivation. In the area labeled Immunity any ferrous ions
in solution would be plated back on the metal (i.e.) iron is
thermodynamically stable in water in this region. In the area
labelled corrosion the corrosion product is either ferrous or
f e r r i c ion in solution. In the area labelled passivation the iron
Q

CORROSION
130
CHEMISTRY
is supposed to be covered by a s o l i d f i l m of F e 0 or FeaO^ which

stops c o r r o s i o n completely. Dashed l i n e (b) is the e q u i l i b r i u m
p o t e n t i a l f o r 0 and (d) f o r H .
The Pourbaix diagram, w i t h i n i t s assumptions gives a good
general p i c t u r e of i r o n c o r r o s i o n behavior. However i t cannot be
a p p l i e d to s p e c i f i c s i t u a t i o n s f o r a number of reasons. Iron can
form a l a r g e number of s o l i d c o r r o s i o n products with water inc l u d i n g hydrated and anhydrous oxides as w e l l as i l l - d e f i n e d gels
and amorphous products. Some of these may form p r o t e c t i v e coatings w h i l e others w i l l not.
The s o l i d products formed may be
porous and lead to p i t t i n g , cracking, e t c . We must always remember that in a l l regions other than that l a b e l l e d immunity the
i r o n is thermodynamically unstable and in the long run nature w i l l
have i t s way and the metal w i l l corrode.
The a d d i t i o n of other ions to the s o l u t i o n , while probably
having a small e f f e c t on the o v e r a l l thermodynamics of the s i t u a t i o n can have a very l a r g
on the k i n e t i c s of d i s s o l u t i o
case of c h l o r i d e s , lead to l o c a l i z e d attack by breakdown of prot e c t i v e f i l m s . In t h i s way although the most of the metal surface
follows the behavior p r e d i c t e d by the Pourbaix diagram, d i s s o l u t i o n at confined areas leads to f a i l u r e by p i t t i n g or cracking.
The Pourbaix diagrams a l s o t e l l one very l i t t l e about
mechanism of r e a c t i o n , k i n e t i c s of r e a c t i o n or i n h i b i t i o n of r e a c t i o n . These aspects w i l l be d e a l t with in the r e s t of t h i s
chapter.
2
Electrochemistry
and
Corrosion
M a t e r i a l s can d i s s o l v e by d i r e c t d i s s o l u t i o n or by separate
steps.
An example of the former is the d i s s o l u t i o n of sugar in
water and of the l a t t e r the c o r r o s i o n of i r o n in aqueous solutions,.
D i r e c t d i s s o l u t i o n or i r o n may occur in some organic solvents
and in the presence of some c o n s t i t u e n t s in aqueous s o l u t i o n s .
In most aqueous c o r r o s i o n systems i r o n (and most other metals)
goes i n t o s o l u t i o n v i a an e l e c t r o c h e m i c a l process in which there
are separate anodes and cathodes. In a de-aerated s o l u t i o n the
separate r e a c t i o n s are
2+
Fe
*Fe
2H + 2e
+ 2e
->H
2
(anode)
(cathode)
In the presence of oxygen the o v e r a l l cathodic

0
+ 2H 0 + 4e
2
40H~
reaction
is
(cathode)
I f we measure the p o t e n t i a l of the d i s s o l v i n g iron,we w i l l

not o b t a i n an e q u i l i b r i u m p o t e n t i a l (as in the Pourbaix diagram)
but a value somewhere between the anodic and cathodic p o t e n t i a l s .
T h i s number w i l l depend on such f a c t o r s as how the p o t e n t i a l s

5.
COHEN
Dissolution
of
Iron
131
change with c u r r e n t , ( i . e ) the slopes of the p o l a r i z a t i o n curves,

the various r e s i s t a n c e s in the system, and d i f f u s i o n of reactants
and r e a c t i o n products.
With i r o n the slope of the anodic p o l a r i z a t i o n curve is considered to be much l e s s than that of the
cathodic curves.
With these considerations in mind U.R. Evans
suggested what are now known as the Evans* diagrams to describe
the e l e c t r o c h e m i c a l mechanism of c o r r o s i o n . T y p i c a l curves f o r
i r o n are shown in Figure 4,
(2).
In Figure 4 the top curves with the downward slopes are f o r
cathodic r e a c t i o n s . In 4(a) are shown curves f o r anodic and
cathodic r e a c t i o n which are only c o n t r o l l e d by a c t i v a t i o n p o l a r i z a t i o n . A t y p i c a l example is a w e l l s t i r r e d a c i d s o l u t i o n .
The
top cathodic curve is f o r oxygen and the lower one f o r hydrogen.
Obviously the p o s s i b l e c o r r o s i o n r a t e in the presence of oxygen
is higher than that in the presence of hydrogen only.
Because
of t h i s oxygen is sometimes c a l l e d a good cathodic d e p o l a r i z e r .
In 4(b) and 4(c) are show
d i f f u s i o n c o n t r o l . In (b
caused by a low concentration of oxygen from the bulk of the
s o l u t i o n . In (c) high anodic p o l a r i z a t i o n may be caused by slow
d i f f u s i o n of ferrous ions away from the anode. With both (b) and
( c ) , the p o l a r i z a t i o n curves and hence the d i s s o l u t i o n r a t e w i l l
be h i g h l y dependent on concentration and s t i r r i n g . With (c) i r o n
i o n complexing agent w i l l a l s o markedly a f f e c t the r a t e of d i s s o l u t i o n by i n c r e a s i n g the d i f f u s i o n r a t e by i n c r e a s i n g the concentration gradient.
The p o l a r i z a t i o n curves shown in 4(d) are t y p i c a l of systems
in which anodes and cathodes are separated by c o r r o s i o n products
and/or s o l u t i o n s of some r e s i s t a n c e . The c o r r o s i o n r a t e (current
density) depends on the average r e s i s t a n c e between the anodes and
cathodes and the p o t e n t i a l which is measured depends on the
p o s i t i o n of the probe e l e c t r o d e in r e l a t i o n to the r e s i s t a n c e
separating the anode and cathode. In a corroding system of t h i s
type there is a current flowing through the s o l u t i o n which can be
c a l c u l a t e d by measuring the p o t e n t i a l d i f f e r e n c e s between two
spaced e l e c t r o d e s in the s o l u t i o n and the r e s i s t a n c e of the
s o l u t i o n . Evans and h i s co-workers d i d t h i s with i r o n in b i c a r bonate s o l u t i o n s and showed that a l l the c o r r o s i o n could be
accounted f o r by the currents flowing between anodes and cathodes,
(3) . T h i s confirmed the e l e c t r o c h e m i c a l mechanism of c o r r o s i o n .
Mechanisms of Reactions
Although the o v e r a l l anodic and cathodic r e a c t i o n s are those
given in Equations 1-3,it is u s u a l l y considered that the r e a c t i o n s
take p l a c e in a s e r i e s of steps, one of which is the Rate Determining Step. The most widely accepted anodic scheme is that proposed by K e l l y (4J and is p a r t i c u l a r l y a p p l i c a b l e in a c i d s o l u t i o n s . The r e a c t i o n steps are as f o l l o w s .

132
Figure S.
pH
10
12
14
16
Pourbaix diagram for iron in water
Figure 4. Evans-type polarization curves: (a) anodic curve intersecting two pos
sible cathode reactions; (b) diffusion control of cathodic reaction; (c) diffusion
control of anodic reaction; and (d) resistance pohrization, measure will depend
on where probe is in relation to anode and cathode

COHEN
5.
Dissolution
Fe + H 0
of
133
Iron
^Fe(H 0) adsorbed
Fe(H 0)ads
^Fe(OH~)ads +
<
>(FeOH)ads + e
Fe(0H~)ads
(FeOH) + H
Fe(OH)ads
+
KFeOH) * + e
+
=^
44
Fe " +
RDS
H0
2
This mechanism postulates that the electron transfer step takes

place in two stages with the oxidation of (FeOH)ads being the
rate determining step(RDS).
In the presence of halides there is a change in mechanism
and Lorenz (j) has suggested the following steps.
Fe + H 0
<
> Fe(H 0)ads
Fe(H 0)ads + X~ *
2
ad
FeX~
+ 0H~
FeOH* + X" + 2e
ads
Fe0H+ + H ^=5- Fe " + H 0
o
RDS
44
Here the oxidation involves an adsorbed halide iron-surface metal

atom complex. In both cases oxidation is to ferrous ion in
solution. The f i n a l concentration of FeOff* and Fe""" is strongly
pH dependent. The two ions w i l l only be stable in acid or oxygenfree systems. In the presence of oxidants the Fe""* w i l l be oxidized to various insoluble ferric compounds such as FeaO^.
Fe20
and the hydrated oxides, a, 3 and FeO(OH).
The two main cathodic reactions involved in dissolution
(and corrosion) reactions are the reduction offf*"to H and the
reduction of dissolved 0 to OH".
The following reaction schemes
are the ones which have been postulated.
-
4 1
H
H
+e
aq
or H 0 + e
2
+
H
Reduction
,
ads
. + OH
ads
aq
+ ads + e
aq
H0 - + e
2
ads
-
1(a)
2
3
+ 0H_.
3(a)
aq
(1) and (3) w i l l predominate over 1(a) and 3(a) at low ph s. The
rate determining step depends in part on the catalytic properties
of the surface. This is particularly true for the recombination
reactions (2) and 3 or 3(a). In some cases the recombination re
action is more d i f f i c u l t than dissolution of atomic hydrogen into
the metal and an alternative reaction
o
(1)

134
H
metal
ads
(4)
becomes a predominant r e a c t i o n .
I f c a t a l y t i c s i t e s f o r hydrogen
atom recombination e x i s t w i t h i n the metal, such as i n c l u s i o n s ,
then hydrogen gas is formed in the metal and b l i s t e r i n g and rup
ture can occur.
0^ Reduction
0
0
+ e
+ H
0 ads.
2
H0 ads.
2
H0
+ e"
H0
H0
+ H~*
22ads
OH + e
+ 2H
+ 2e
H 0 .
2 2 aq
2H 0.
2H 0.
+ 4H
OH" + 4H+ + 4e
+ 4e~
^2H 0.
2
H2O2 has been i d e n t i f i e d as a t r a n s i e n t species.

These r e a c t i o n s
are a l l q u i t e r a p i d in comparison to the hydrogen e v o l u t i o n r e
a c t i o n and hence the oxygen is a b e t t e r cathodic d e p o l a r i z e r
than H+ i o n .
K i n e t i c s of D i s s o l u t i o n
The r a t e s of both chemical and e l e c t r o c h e m i c a l r e a c t i o n s a r e
a f f e c t e d by the a v a i l a b i l i t y o f the reactants and products, and
hence t h e i r concentrations and rates of d i f f u s i o n , and by a term
known as the a c t i v a t i o n energy f o r the r e a c t i o n .
The r a t e o f an
e l e c t r o c h e m i c a l r e a c t i o n can a l s o be a f f e c t e d by the various r e
s i s t a n c e s in the system.
I f we can s e t up a system in which the r e a c t i o n is not con
t r o l l e d by e i t h e r d i f f u s i o n or r e s i s t a n c e , the r a t e o f the r e
a c t i o n w i l l be determined by the a c t i v a t i o n o v e r - p o t e n t i a l .
This
follows from the Arrhenius equation which states that
k = A exp (-AG*/RT)
where k is the r e a c t i o n r a t e , A is a constant, AG* is the a c t i v a
t i o n energy, R the gas constant and the absolute temperature.
As pointed out e a r l i e r AG* can be r e l a t e d to p o t e n t i a l by the r e relation
AG* = nFAE*

5.
COHEN
Dissolution
135
of Iron
where * is the A c t i v a t i o n o v e r p o t e n t i a l .
The a p p l i c a t i o n o f
p o t e n t i a l to the e l e c t r o d e w i l l t h e r e f o r e increase the r a t e o f
e i t h e r the forward or reverse r e a c t i o n .
A schematic a c t i v a t i o n energy diagram f o r a r e a c t i o n is
shown in F i g . 5. The dotted l i n e represents the e q u i l i b r i u m
s t a t e and the s o l i d l i n e a p o l a r i z e d s t a t e due to an a p p l i e d
potential.
In the e q u i l i b r i u m s t a t e
_AG*
*a
a ^RT*
_AG*
where s u b s c r i p t s a and c a r e anodic and cathodic and i

- where i is the exchange current.
When a p o t e n t i a l
is a p p l i e d in an anodi
= i ^= i
a
,
(AGa-nFE)
then = + A e (
-)
a
a
RT
and
A i = A e -(AGc (l-a)nFE)
C
C
RT
'
l
where a is the p r o p o r t i o n of the a p p l i e d p o t e n t i a l which is

e f f e c t i v e at the anode. As a r u l e = 0.5. The e f f e c t of the
a p p l i e d anodic p o t e n t i a l is to increase i and decrease i . For
the t o t a l current we must add i .
However at s u f f i c i e n t l y high
o v e r p o t e n t i a l s both i and i become small in r e l a t i o n to and
a
= a + b logi .
(Tafel
equation).
Some o f these r e l a t i o n s h i p s a r e i l l u s t r a t e d g r a p h i c a l l y in
Figure 6. E is the e q u i l i b r i u m p o t e n t i a l . At s u f f i c i e n t l y
high o v e r p o t e n t i a l s a s t r a i g h t l i n e T a f e l region is observed.
At higher a p p l i e d p o t e n t i a l s current may become independent of
p o t e n t i a l because of d i f f u s i o n c o n t r o l or may f a l l o f f the
s t r a i g h t l i n e due to r e s i s t a n c e p o l a r i z a t i o n . In the anodic r e
a c t i o n t h i s is u s u a l l y due to the formation o f f i l m s on the sur
face of the metal.
These concepts can be a p p l i e d q u i t e d i r e c t l y to the c o r r o
s i o n behavior of i r o n . The e f f e c t of d i f f u s i o n c o n t r o l on the
c o r r o s i o n r a t e was shown in the Evans Diagrams (b) and (c) of
F i g u r e 4. In the cathodic case the current becomes constant over
a wide range of p o t e n t i a l s because of c o n t r o l by the r a t e o f
d i f f u s i o n o f the reactant oxygen gas to the cathode. The anodic
r e a c t i o n can be dependent on the r a t e of d i f f u s i o n of e++ from
the anode. The r a t e s in both cases can be increased by s t i r r i n g .
The r a t e of Fe** i o n removal from the anode can a l s o be in
creased by the presence of complexing agents in the s o l u t i o n .
This e f f e c t w i l l be i l l u s t r a t e d l a t e r on with i n h i b i t o r s .
Q

136
Figure 5. Activation energy diagrams for metal dissolution reaction.

rium state (
); shift attributable to application of potential (
RESISTANCE
POLARIZATION
CONCENTRATION
POLARIZATION
(DIFFUSION CONTROL)
Log i
EXCHANGE CURRENT
CATHODIC Figure 6.
ANODIC
Polarization curves for anodic reactions

Equilib
).
5.
COHEN
Dissolution
of Iron
137
The effect of the formation of films under some anodic

conditions has been known and studied for many years. Millier (j6)
observed that at high applied potentials salt films could form
at the anode which would reduce the current density. When these
films diffused away,the current rose again. This is a case of
intermittent resistance polarization. In some solutions i t is
possible to stop iron from dissolving under some conditions. Two
of these sets of conditions are illustrated in Fig. 7. In Fig.
7(a) the current density is raised in steps. The potential cur
rent relationship starts out in the normal way but at a s u f f i
ciently high current density a sudden discontinuity occurs in
the log i-E curve with a sharp rise of potential. At the same
time the metal stops dissolving and a second anodic reaction
such as oxygen evolution takes over. This type of behavior was
f i r s t shown by Edeleanu (7) who also suggested the use of anodic
protection to prevent corrosion. In Fig. 7(b) the potential is
raised in steps. Again
sharply and iron stops
a wide range of potential. This type of behavior is characteris
t i c of iron over a wide range of pH conditions and has been
studied extensively. It is of interest not only for anodic pro
tection but also for understanding the action of anodic inhibi
tors. This passive condition is not something that would be
predicted from kinetic considerations and is probably due to the
formation of a solid protective phase over the iron which slows
down the reaction.
Passivation of Iron
(a) Electropolishing. The deviation from the theoretical
anodic dissolution behavior can be used to advantage in several
ways. One of these is for the electropolishing of iron. An
anodic polarization curve for iron in a perchloric-acetic acid
solution is shown in the Fig. 8. It can be seen that there are
three regions of the curve. In the f i r s t region, A, the log i-E
curve is the expected one and the iron dissolved in a general way
with macro etching. In Region the current changes very l i t t l e
with potential and the specimen smooths. This is probably due
to the formation of film which is resistant to cation movement
from the metal. At higher potentials, RegionC.,this film breaks
down locally and the specimen dissolves by a combination of
smoothing and pitting. Region can be considered as a region of
passivation in that the dissolution is less than would be ex
pected from the overpotential. Under some conditions this anodic
dissolution can be made very small and the specimen is considered
to be anodically passivated.
(b) Anodic Passivation. Anodic passivation can be obtained
over a wide range of pH s and in a variety of electrolytes. In
this section, however, I shall deal mainly with neutral solutions
f

138
(a)
Figure 7.
(b)
Anodic passivation curves
6.0
20
Figure 8.
40
60
80
CELL POTENTIAL-volts
100
120
Anodic dissolution in perchloric-acetic
acid

5.
COHEN
Dissolution
of
Iron
139
because, f i r s t , i t is the medium in which I have done most of my

own work and second, because r e s u l t s in t h i s range are most
a p p l i c a b l e to l a t e r c o n s i d e r a t i o n s of p a s s i v i t y in i n o r g a n i c in
h i b i t o r systems.
In F i g . 9 three p o l a r i z a t i o n curves f o r i r o n in b u f f e r e d
sodium borate s o l u t i o n s are shown. In A the s o l u t i o n was sodium
b o r a t e - b o r i c a c i d at a pH of 8.4 (8). The curve was obtained by
p o l a r i z i n g i r o n at a constant p o t e n t i a l and measuring the current
a f t e r 20 minutes. S t a r t i n g with an o x i d e - f r e e specimen the
current f i r s t increases as the p o t e n t i a l is increased, reaches a
maximum and then decreases again.
There is a r e g i o n of over a
v o l t in which i r o n does not d i s s o l v e , or is p a s s i v e , and then the
current r i s e s again, due mainly to oxygen e v o l u t i o n . In the
passive region the i r o n is covered by a t h i n f i l m of cubic oxide
of the y-Fe203-Fe30i* type which is probably formed by a r e a c t i o n
such as
2Fe + 3H 0 ->
2
T h i s is the same type of f i l m as is formed by the r e a c t i o n of

clean i r o n with dry a i r or oxygen.
For Curve the s o l u t i o n was sodium c h l o r i d e - b o r i c a c i d
b u f f e r e d to pH 7.8.
The p o l a r i z a t i o n c o n d i t i o n s were the same.
However in the presence of the c h l o r i d e the maximum current be
f o r e the onset of p a s s i v i t y was increased and the p o t e n t i a l range
for p a s s i v i t y was decreased. The high currents observed in the
"passive r e g i o n " were mainly due to l o c a l i z e d a t t a c k which leads
to p i t t i n g .
The major part of the s u r f a c e is s t i l l covered by
the same type of i r o n oxide f i l m as that found with the pure
borate b u f f e r .
A t h i r d type of anodic p o l a r i z a t i o n curve, C., is obtained
i f the borate b u f f e r s o l u t i o n contains Fe** i o n in s o l u t i o n .
This may be present as an added Fe** s a l t or due to some d i s
s o l u t i o n of the specimen during p a s s i v a t i o n . In t h i s case the
passive current is again higher than in the borate b u f f e r i t s e l f .
This is due to the anodic o x i d a t i o n of the d i s s o l v e d Fe** at the
e l e c t r o d e and the consequent d e p o s i t i o n of yFeOOH on the i r o n
s u r f a c e . The anodic r e a c t i o n is
Fe(OH)* + H 0
2
+ FeO (OH)
+ 2H
e.
T h i s deposit is formed over the oxide f i l m as w e l l as at pores

w i t h i n the oxide f i l m .
The d i s s o l u t i o n of i r o n by c o r r o s i o n processes almost always
takes p l a c e because of f i l m breakdown and the r a t e of c o r r o s i o n
depends not only on the thermodynamic and k i n e t i c c o n s i d e r a t i o n s
mentioned in the f i r s t part of t h i s chapter but a l s o on the f a c
t o r s leading to f i l m breakdown and r e p a i r . This is the subject
of the l a s t part of t h i s chapter.

CORROSION
140
F i l m Breakdown and
CHEMISTRY
Repair
When f i l m f r e e i r o n is exposed to dry a i r or oxygen at room

temperature, i t w i l l form a p r o t e c t i v e f i l m of a cubic oxide of
the FeaOtt-yFeaOa type which grows l o g a r i t h m i c a l l y to about 15-20
A t h i c k . This is the same type of f i l m as is formed by anodic
p a s s i v a t i o n and by the a c t i o n of c e r t a i n oxidants in s o l u t i o n .
Under other c o n d i t i o n s the o v e r a l l composition of t h i s cubic f i l m
can be a l t e r e d by the a d d i t i o n of hydrated oxides or other i n s o
l u b l e oxides, such as C r 0 , which can change the thickness, topo
graphy and s t a b i l i t y of the o v e r a l l f i l m .
In some cases these
i m p u r i t i e s are present as separate i n c l u s i o n s w i t h i n the f i l m
l e a d i n g to weakened areas at which l o c a l i z e d breakdown may occur
or they may be on top of the cubic oxide f i l m , such as a depo
s i t e d -FeOOH and enhance the p r o t e c t i v e n e s s of the f i l m .
These
various cases are discussed in t h i s s e c t i o n .
2
Structure of the Oxide

The major p o r t i o n of the p r o t e c t i v e oxide f i l m on i r o n is
s t r u c t u r a l l y the same whether i t is grown by exposure to a i r ,
i n h i b i t o r s o l u t i o n s or formed by anodic o x i d a t i o n 9,1Q). I t is
cubic in nature and grows in an e p i t a x i a l manner with the underl y i n g metal. Although the oxide formed on s i n g l e c r y s t a l s is
h i g h l y oriented, there is some mismatch between i n d i v i d u a l c r y s t a l l i t e s and the p a r t i c l e s i z e is 15-30A . The thickness of the
air-formed f i l m at room temperature is 15-20 A . The f i l m s
formed a n o d i c a l l y in n e u t r a l s o l u t i o n can be up to 40 A in
thickness, the thickness i n c r e a s i n g with higher p o l a r i z a t i o n
p o t e n t i a l s . An e l e c t r o n d i f f r a c t i o n p a t t e r n of the oxide on
s i n g l e c r y s t a l s of i r o n is shown in F i g . 10.
T h i s shows the very
ordered s t r u c t u r e as w e l l as the broadened spots due to small
p a r t i c l e s i z e . The p a t t e r n is c h a r a c t e r i s t i c of the cubic FeaO^Y F e 0 system. This system has a constant face-centered cubic
l a t t i c e of oxygen with varying amounts of i r o n in both o c t a h e d r a l and t e t r a h e d r a l p o s i t i o n s . The oxide probably v a r i e s in
composition from the metal-oxide i n t e r f a c e to the oxide-gas or
s o l u t i o n i n t e r f a c e with the yFe203 at the o u t s i d e .
Under some c o n d i t i o n s the f i l m w i l l contain i n c l u s i o n s of
other i r o n compounds, such as hydroxides or phosphates, and as
mentioned e a r l i e r may a l s o have an overlay of p r e c i p i t a t e d or dep o s i t e d compounds.
0
Breakdown of
Films
In general, oxide f i l m s can be removed as p r o t e c t i v e l a y e r s

by chemical d i s s o l u t i o n , undermining, or cathodic r e d u c t i o n .
Anhydrous oxide f i l m s are u s u a l l y q u i t e d i f f i c u l t to d i s s o l v e . The r a t e of s o l u t i o n increases with lower pH and higher
temperature. In n e u t r a l s o l u t i o n the r a t e of d i s s o l u t i o n of the

COHEN
Dissolution
of
Iron
- CHLORIDE-BORATE
SOLUTION
Lu
or
or
10 f-
-800
-400
20
400
800
1200
POTENTIAL vs. S.C.E.

Figure 9.
Figure 10.
Anodic polarization curves in borate buffer solutions
Electron diffraction pattern of thin cubic oxide film on iron

142
passive f i l m is so slow that i t is probably not a f a c t o r in the

breakdown of oxide f i l m s on i r o n . The hydrated oxides are more
e a s i l y d i s s o l v e d , e s p e c i a l l y in s l i g h t l y a c i d s o l u t i o n s and t h e i r
removable by d i s s o l u t i o n could be a d e f i n i t e f a c t o r in f i l m break
down. I f the f i l m has pores in i t which expose the metal to the
c o r r o s i v e s o l u t i o n , t h e metal can d i s s o l v e both at the bottom of
the pore and between the f i l m and the metal. T h i s l a t t e r e f f e c t
loosens the oxide by undermining and e v e n t u a l l y leads to i t s
removal.
U.R. Evans took advantage of t h i s phenomenon to s t r i p
oxides from i r o n f o r chemical and p h y s i c a l examination ( 1 1 ) . To
prevent cathodic r e d u c t i o n of the oxide he made the system anodic.
The major cause of removal of oxide f i l m s on i r o n is the
r e d u c t i v e d i s s o l u t i o n of the oxides. The anodic current f o r the
process may be s u p p l i e d by an o u t s i d e source or by areas of the
metal at which i r o n is d i s s o l v e d . In both cases the f e r r i c oxide
is reduced to Fe ".
The s o l u b i l i t y of Fe(0H) is much higher than
e i t h e r F e 0 , FeaO^ or
t i t e component o f the oxid
to Fe metal.
The cathodic r e d u c t i o n of an a n o d i c a l l y formed oxide f i l m is
shown in F i g u r e 11. The f i l m was formed by anodic o x i d a t i o n in
a n e u t r a l sodium borate s o l u t i o n .
I t was c a t h o d i c a l l y reduced in
the same s o l u t i o n , in the absence of oxygen, at /cm . Two
major waves a r e observed.
F i r s t the F e 0 is reduced with almost
100% current e f f i c i e n c y to form d i s s o l v e d Fe** i o n . The second
wave corresponds to an i n e f f i c i e n t r e d u c t i o n of Fe30i* to form both
s o l u b l e Fe** i o n and m e t a l l i c i r o n . The equations f o r these pro
cesses are
44
1st A r r e s t Y F e ^ + 3H 0 + 2e
2
2Fe
+ +
+ 60H~
(A)
2nd A r r e s t F e 0 , + 4H 0 + 8e
Fe + 80H~
(B)
3 4
2
F e 0 . + 4H 0 + 2e
3Fe** + 80H~
(C)
3 4
2
During the second a r r e s t there is a l s o c o n s i d e r a b l e hydrogen evol u t i o n form the a l t e r n a t e cathodic r e a c t i o n
2H
+ 2e
H .
2
I f the r e d u c t i o n process is c a r r i e d on f o r a long time,there is

a l s o some e l e c t r o d e p o s i t i o n of i r o n from Fe** in the s o l u t i o n .
The major source of e l e c t r o n s f o r the cathodic r e d u c t i o n pro
cess on open c i r c u i t is the c o r r o s i o n of the i r o n i t s e l f .
These
are s u p p l i e d by the r e a c t i o n
Fe
44
F e " + 2e
The p o t e n t i a l f o r t h i s r e a c t i o n is more negative than that f o r r e

a c t i o n (A) and hence the e l e c t r o n s are a v a i l a b l e f o r the r e d u c t i v e
d i s s o l u t i o n of y F e 0 3 . On open c i r c u i t the oxide can be removed
2

5.
COHEN
Dissolution
of
143
Iron
by a combination of r e d u c t i v e d i s s o l u t i o n to open up pores and

undermining to remove the remaining Fe O and unreduced f i l m .
The rates of d i s s o l u t i o n of Fe O and the hydrated oxides
both i n c r e a s e q u i t e q u i c k l y w i t h decrease in pH.
Hence breakdown
of f i l m s is more r a p i d in a c i d s o l u t i o n s . I t is a l s o more r a p i d
in s o l u t i o n s c o n t a i n i n g ions which l e a d to a c i d formation in the
anodic pores.
C h l o r i d e i o n is the most damaging of t h i s type of
i o n although sulphates are a l s o d e s t r u c t i v e . The i r o n c h l o r i d e
s a l t s which form during c o r r o s i o n in the pores hydrolyse to give
p r e c i p i t a t e d i r o n s a l t s and a c i d . C h l o r i d e may a l s o act
somewhat l i k e a complexing agent to i n c r e a s e the c o r r o s i o n r a t e .
The e f f e c t of various ions on f i l m breakdown was r e c e n t l y d i s cussed at a symposium on p a s s i v i t y (12).
3
I n h i b i t i o n of
tt
it
Corrosion
I n h i b i t o r s can slo
with e i t h e r the anodic
h i b i t o r s can be e f f e c t i v
y
poisoning
hy
drogen e v o l u t i o n and/or oxygen r e d u c t i o n or by i n c r e a s i n g e l e c t r o n i c r e s i s t a n c e . Some examples are z i n c s a l t s which form prec i p i t a t e s , adsorbing organic substances and p o s s i b l y the p o l y phosphates under some c o n d i t i o n s . The d i s c u s s i o n in t h i s l e c t u r e
w i l l deal mainly with anodic i n h i b i t o r s .
These act by i n t e r f e r i n g
with the anodic d i s s o l u t i o n - p r o c e s s by a s s i s t i n g in the formation
and p r e s e r v a t i o n of an oxide f i l m , s i m i l a r to that produced during
anodic o x i d a t i o n of i r o n .
Anodic I n h i b i t o r s
The anodic i n h i b i t o r s are u s u a l l y i n o r g a n i c s a l t s which,
above a minimum c o n c e n t r a t i o n decrease c o r r o s i o n to a n e g l i g i b l e
amount. A t y p i c a l c o n c e n t r a t i o n versus weight-loss curve is shown
f o r sodium n i t r i t e in F i g u r e 12.
In the absence of i n h i b i t o r or
very low concentrations the c o r r o s i o n is l o c a l i z e d and takes the
form of p i t t i n g . At s u f f i c i e n t l y high concentration the i r o n is
completely p r o t e c t e d . T h i s phenomenon of p i t t i n g at concentrations j u s t below that r e q u i r e d f o r i n h i b i t i o n is important and must
be taken i n t o account when anodic i n h i b i t o r s are used. The conc e n t r a t i o n of i n h i b i t o r r e q u i r e d to stop c o r r o s i o n is dependent on
the composition of the s o l u t i o n and is u s u a l l y decreased by the
presence of oxygen and increased by a d d i t i o n s of c h l o r i d e or
complexing agents. The e f f e c t of a strong complexing agent, v e r sene, is shown in Figure 13.
The time required to achieve i n h i b i t i o n , as measured by the attainment of a passive p o t e n t i a l is
increased as the concentration of complexing agent is increased.
The complexing agent keeps the i r o n in s o l u t i o n and prevents the
r e p a i r of pores by d e p o s i t i o n of f e r r i c s a l t s .
The c l o s e connection between p o t e n t i a l and c o r r o s i o n is shown
by the two s e t s of graphs in F i g u r e 14.
Here one can see, that
f o r i r o n in phosphate s o l u t i o n in the presence of oxygen, the time

-400
CATHODIC REDUCTION CURVE FOR 1 hr
ANODIZED SPECIMEN AT + 6 0 0 mV
500
> -600
-J
C -700 -
_o
',
CATHODIC CURRENT 10 A/cm

BORIC ACID-BORATE
g - 800
-900HI
-1000
Figure 11.
20
30
40
QUANTITY OF ELECTRICITY mC
50
Cathodic reduction of anodically formed oxide film on iron
1200
-GENERAL CORROSION
lOOppmKCI IN AERATED
DISTILLED WATER
, 800
PITTING
400 1
INHIBITION
10
20
30
40
50
60
70
80
ppm SODIUM NITRITE

Figure 12.
Inhibition of corrosion by sodium nitrite

90
COHEN
Dissolution
of Iron
TIME-HOURS
Figure 13. Effect of complexing agent, versene, on passivation by sodium
nitrite: (A) etched iron in NaN0 solution; (B) same as in A plus versene
2

146

Figure 14.
Rehtionship between corrosion and potential in neutral phosphate

solutions: (A) deaerated solution; (B) air saturated (10)

COHEN
5.
Dissolution
of
147
Iron
at which the p o t e n t i a l r i s e s to the passive r e g i o n is a l s o the

time at which c o r r o s i o n ceases.
In the absence of oxygen c o r r o s i o n continues and the p o t e n t i a l remains in the a c t i v e r e g i o n .
The n e c e s s i t y f o r the presence of oxygen f o r i n h i b i t i o n is
common to a l a r g e number of i n o r g a n i c substances.
In general
these are n o n - o x i d i z i n g s a l t s which have some b u f f e r i n g c a p a c i t y
in the n e u t r a l r e g i o n . There is a l s o a group of anodic i n h i b i t o r s which are o x i d i z i n g agents and i n h i b i t in both the presence
and absence of oxygen. The o x i d i z i n g agents i n h i b i t at a much
lower concentration than the n o n - o x i d i z i n g agents in the presence
of oxygen (13). This is shown in F i g u r e 15.
P o t e n t i a l time curves f o r the same s e r i e s of i n h i b i t o r s are shown in t h i s F i g u r e .
The p o t e n t i a l s f o r the n o n - o x i d i z i n g i n h i b i t o r s in the absence of
oxygen reach a steady value f o r i r o n in a saturated s o l u t i o n of
Fe""*" at a concentration c h a r a c t e r i s t i c of the pH of the s a l t
s o l u t i o n . The p o t e n t i a l of the o x i d i z i n g i n h i b i t o r s is somewhat
higher and with s u f f i c i e n
c h a r a c t e r i s t i c of oxide-covere
shown in t h i s F i g u r e , but the p o t e n t i a l of i r o n in de-aerated
s o l u t i o n goes i n t o the p a s s i v e r e g i o n very r a p i d l y . U n t i l r e c e n t l y chromate was the p r e f e r r e d i n h i b i t o r f o r many a p p l i c a t i o n s .
However chromate is undesirable from an environmental standpoint
and there is renewed research and development in the use of n i t r i t e , molybdate and small concentrations of phosphate.
There is another group of i n h i b i t o r s which act by adsorption
onto e i t h e r the metal or the oxide. These are u s u a l l y organic
m a t e r i a l s and the most e f f e c t i v e are e i t h e r a l c o h o l s or amines.
They are mainly used in s p e c i a l i z e d a p p l i c a t i o n s such as i n h i b i t i o n of a c i d c o r r o s i o n during p i c k l i n g or in m i t i g a t i o n of c o r r o s i o n in a c i d o i l w e l l s . The exact a c t i o n of these i n h i b i t o r s is
beyond the scope of t h i s chapter but they are discussed by
Hackerman and others (14). Some b u f f e r i n g i n h i b i t o r s , such as
sodium benzoate may a l s o act by adsorption on the s u r f a c e .
1
Localized
Corrosion
In the d i s c u s s i o n to t h i s point we have noted three cases

where the c o r r o s i o n occurred in a l o c a l i z e d manner v i a p i t t i n g .
These were in an e l e c t r o p o l i s h i n g s o l u t i o n at a current d e n s i t y
(and p o t e n t i a l ) higher than in the p o l i s h i n g r e g i o n , in a borate
b u f f e r s o l u t i o n c o n t a i n i n g c h l o r i d e at a p o t e n t i a l a few hundred
m i l l i v o l t s higher than the p a s s i v a t i o n p o t e n t i a l , and in i n h i b i t o r
s o l u t i o n s at j u s t below the concentration of i n h i b i t o r r e q u i r e d to
prevent c o r r o s i o n . In a l l of these examples the major p o r t i o n of
the specimen is covered with the usual FesOt* - y F e 0 type of prot e c t i v e f i l m and c o r r o s i o n is concentrated at pores w i t h i n t h i s
film.
The c o r r o s i o n at the anodic pores is a c c e l e r a t e d by the
l a r g e area covered by p r o t e c t i v e f i l m a c t i n g as a cathode. T h i s
breakdown of the p r o t e c t i v e f i l m at i s o l a t e d areas is an important
f a c t o r in two of the most damaging types of c o r r o s i o n f a i l u r e ,
2
American Chemical
Society Library
1155
16th
St.
Washington, D. C.
N. W,
20038


Figure 15.
Inhibition in both oxidizing and nonoxidizing inhibitors. Weight-loss data in aerated

solutions. Electrode potential curves in absence of oxygen (13).
5.
COHEN
Dissolution
of
Iron
149
namely the p e r f o r a t i o n of metal by p i t t i n g and s t r e s s c o r r o s i o n

cracking.
Examples of p i t t i n g in phosphate s o l u t i o n s w i t h d i f f e r e n t
c h l o r i d e contents are shown in Figure 16.
Two things are evident.
F i r s t , the l a r g e r the c h l o r i d e concentration the l a r g e r the p i t s .
Second, the number of p i t s is dependent on the g r a i n s t r u c t u r e .
This l a t t e r f a c t would i n d i c a t e that the p e r f e c t i o n of the oxide
is p a r t i a l l y dependent on the metal o r i e n t a t i o n . The dependence
of p i t behavior on s t i r r i n g of the s o l u t i o n is shown in F i g u r e 17.
Here one can see that s t i r r i n g causes an increase in the p o t e n t i a l
of i r o n in n i t r i t e s o l u t i o n s . This is probably due to the lowering of cathodic p o l a r i z a t i o n by i n c r e a s i n g the r a t e of oxygen and
n i t r i t e a r r i v a l at the cathode. This increase in cathodic curent appears to a i d the r e p a i r of the pore. In contrast to t h i s
behavior, s t i r r i n g decreases the p o t e n t i a l of the p i t t e d s p e c i men in phosphate s o l u t i o n . T h i s i n d i c a t e s that s t i r r i n g leads to
d e p o l a r i z a t i o n of the anodi
s i o n products at the p i t s
general, the p o t e n t i a l s with phosphate are lower than with n i t r i t e , i n d i c a t i n g a l a r g e p r o p o r t i o n of a c t i v e areas and hence a
mixed p o t e n t i a l which is c l o s e r to that of the anode.
Stress c o r r o s i o n cracking a l s o i n v o l v e s l o c a l i z e d breakdown
of the p r o t e c t i v e f i l m .
The c o r r o s i o n is narrowly confined within the metal due to s t r e s s f a c t o r s which may a r i s e from e i t h e r
r e s i d u a l i n t e r n a l s t r e s s or a p p l i e d e x t e r n a l s t r e s s . In some
cases the s t r e s s f a i l u r e can be a c c e l e r a t e d by chemical f a c t o r s ,
such as surface adsorption or hydrogen d i s s o l u t i o n from cathodic
hydrogen l e a d i n g to embrittlement.
L o c a l i z e d f i l m breakdown can r e s u l t from a number of causes.
Chemical and p h y s i c a l inhomogeneities w i t h i n the f i l m are the
usual reasons although breakdown can a l s o occur by s t r e s s e s set
up w i t h i n the f i l m e i t h e r by poor e p i t a x i a l f i t of the oxide to
the metal, or as Sato (15) has suggested by equivalent condenser
pressure during anodic growth of the f i l m . Vermilyea (16) has
shown current increases due to the cracking and r e p a i r of f i l m s
during s t r e t c h i n g of passivated i r o n wires. The r o l e of s t r e s s
is s t i l l a subject of a c t i v e research.
Some of the r e a c t i o n s which can take place at imperfections
in f i l m s and which can lead to e i t h e r d i s s o l u t i o n or f i l m r e p a i r
are shown in the f i n a l f i g u r e , Figure 18.
Here a specimen covered
with an oxide f i l m with pores or imperfections is shown. A number
of d i f f e r e n t r e a c t i o n s can take place both at the pores and on
the oxide s u r f a c e .
In general the r e a c t i o n s at the pores r e present e i t h e r anodic or d i s s o l u t i o n processes, while those on the
oxide surface are cathodic in nature. Reaction 1 coupled with
r e a c t i o n s (6) or (7) represents the standard d i s s o l u t i o n process.
This can be a c c e l e r a t e d by a number of f a c t o r s such as lowered
pH, presence of c h l o r i d e and complexing agents. Reaction (1)
coupled with r e a c t i o n (8) gives both d i s s o l u t i o n and removal of
the p r o t e c t i v e f i l m , which w i l l then lead to a c c e l e r a t e d d i s -

150
Corrosion
Figure 16.
Pitting in phosphate-chloride solutions, 1000 ppm Na HPOj ;

ppm CI', (b) 10 ppm C (17)
2

(a) 100
5.
COHEN
Dissolution
151
of Iron
O.I2i
TIME, hr
Corrosion
Figure 17. Effect of stirring on potential of iron in chloride and inhibitor solution: (A) started bubbling; (B) stopped bubbling; 1000 ppm NaN0
+ 100
ppm NaCl; 1000 ppm Na HPO^ + 25 ppm NaCl) (17)
2
HÔ
N0
ATA
Fe
Fe
FeOOH + 3H* + e
(3)
2Fe 0
(4)
4Fe + 3 0
2H
+2e
Fe 0
2
+ H 0 +e
2
+2e+ 3 H 0
2
Figure 18.
^2Fe 0
2
0 + 2 H 0 + 4e
2
+ 6H
(I)
Fe +2H 0
4Fe + N 0 i + 3 H
N0
+ 2e
+ +
Fe 0
+ +
OH"
2Fe + 3 H 0
2
AT C
+ 6e
(2)
+ NH +N (5)
3
(6)
^40H"
(7)
NH
(8)
*~2Fe
(etc)
+ +
+ 60H
(9)
Reaction on film with pore

CORROSION
152
CHEMISTRY
s o l u t i o n . The pores can be r e p a i r e d e i t h e r e l e c t r o c h e m i c a l l y ,

by anodic o x i d a t i o n as in (2) and by anodic d e p o s i t i o n as in
(3).
I t is a l s o p o s s i b l e f o r the f i l m to be r e p a i r e d chemically
by the a c t i o n of i n h i b i t o r s as depicted in r e a c t i o n s (4) and (5).
This type of approach lends i t s e l f to a systematic treatment of
the problems of d i s s o l u t i o n and i t s i n h i b i t i o n .
Literature Cited
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
Pourbaix, M. " A t l a s of E l e c t r o c h e m i c a l E q u i l i b r i u m in
Aqueous S o l u t i o n s " , Pergamon Press, 1966.
Evans, U.R. "An I n t r o d u c t i o n to M e t a l l i c C o r r o s i o n " ,
Edmund A r n o l d Co. London 1948, Pages 71-3.
T h o r n h i l l , R.S. and Evans, U.R. J. Chem. Soc. (1938) 614.
K e l l y , E . J . J. Electrochem. Soc. (1965) 112, 124.
Lorenz, W.J. C o r r o s i o n Science, (1965) 5, 121.
M u l l e r , W.J. Trans
Edeleanu, C. and Gibson
Nagayama, M. and Cohen, M. J. Electrochem. Soc. (1962),
109, 781.
Nagayama, M. and Cohen M. J. Electrochem. Soc. (1963), 110,
670.
Cohen, M. J. Electrochem. Soc. (1974), 121, 191C.
Evans, U.R. and Stockdale, J. J. Chem. Soc. (1929), 2651.
Staehle, R.W. and Okode, H. E d i t o r s . P a s s i v i t y and I t s
Breakdown on Iron and non-Base A l l o y s , U.S.A.-Japan Seminar.
NACE, Houston, Texas. 1976.
Pryor, M.J. and Cohen, M. J. Electrochem. Soc. (1953), 100,
203.
Hackerman, N. and Cook, E . I . J. Phys. Chem. (1952), 56, 524.
Sato, N. E l e c t r o c h i m i c a A c t a . (1971), 16, 1683.
Bubor, S.F. and Vermilyea, D.A. J. Electrochem. Soc. (1966),
112, 882.
Cohen, ., C o r r o s i o n (1976) 32,
461.
R E C E I V E D September 1, 1 9 7 8 .

6
Ferrous Passivation
V. BRUSIC
Manufacturing Research Laboratory, Systems Products Division,
I B M T. J. Watson Research Center, Yorktown Heights, N Y 10598
The progress o
increasing use of tool
bound to lean increasingly on sophisticated computerized
mechanisms to do his work for him with tighter requirements to
function without decay over years in t e r r e s t r i a l atmosphere.
Materials, mainly metals, used in this fabrication must be
stable.
A piece of metal indeed remains stable for an almost
indefinite period of time provided it is stored in vacuum. In
normal t e r r e s t r i a l environments metals become unstable in
various ways: they develop cracks and break upon strain,
suffer fatigue when subjected to periodic stress, undergo a
process of
embrittlement, as well
as react
with the
surroundings.
With the exception of the expensive noble
metals, metallic surfaces are transformed into oxides and
salts which can peel off
or just dissolve away.
Yet
technology predominantly depends on these thermodynamically
unstable, corrosive, non-noble metals, the most widely used
being aluminum, copper, nickel and, of course, iron. They owe
much of their usefulness to the existence of the passive
state.
The passivation phenomenon was f i r s t observed and
described by the action of n i t r i c acid on iron centuries
ago.(1-3)
From then to the present the complexity of the
problem and the practical importance of i t s application has
earned the attention of many scientists.
The present discussion draws particularly on studies that
have been published recently and are concerned with iron
electrodes under conditions producing passivity which are the
ones that best c l a r i f y the passivation process.
Passivation Phenomena
A) Description, Terminology and Some Practical Aspects of
Anodic Protection.
Passivation can be defined as a constant
0-8412-0471-3/79/47-089-153$08.00/0

154
slowing
down of any a c t i o n , process,
or r e a c t i o n .
More
s p e c i f i c a l l y the term is a p p l i e d to the sometimes observed
transformation
of a corroding and
unstable
surface to a
passive and s t a b l e surface by
superimposing a
double-layer
f i e l d which should a c c e l e r a t e the m e t a l - d i s s o l u t i o n r e a c t i o n
r a t h e r than hinder
i t , i.e., by a s h i f t
of the e l e c t r o d e
p o t e n t i a l in the p o s i t i v e d i r e c t i o n .
T h i s phenomenon of
enforced
passivation(4)
seems unnatural
or
at
least
unexpected.
I t s study
is
f a c i l i t a t e d by
the use
of a
potentiostat.
If i r o n is made a part of the e l e c t r o c h e m i c a l c e l l , a
t e s t e l e c t r o d e , and placed in a p o t e n t i o s t a t i c c i r c u i t , Figure
1,
the
experimental
current-potential
plots
show
an
i n t e r e s t i n g p a t t e r n , Figure 2: with
an increase of p o t e n t i a l ,
s t a r t i n g from the c o r r o s i o n p o t e n t i a l , the d i s s o l u t i o n current
i n c r e a s e s , j u s t as expected. Metal ions go i n t o the s o l u t i o n
M > M
2+
2e~
(1
undergoing h y d r a t i o n .
At s t i l l higher p o t e n t i a l s , however,
the curve deviates from simple l o g a r i t h m i c dependence ( T a f e l
law,
metal d i s s o l u t i o n ) . Apparently
metal d i s s o l u t i o n is
hindered
by another process,
that is, the formation
of a
p r o t e c t i v e film,(4) through a r e a c t i o n of the type
M
+ H 0 -> M - 0 + 2H + 2e~
2
(2)
At the p a s s i v a t i o n p o t e n t i a l V a l i m i t i n g p a s s i v a t i o n current
i
is
reached and
the a c c e l e r a t i o n of metal d i s s o l u t i o n is
efjual to the r e t a r d a t i o n of the process.
Above V
the
c u r r e n t - p o t e n t i a l curve
changes d i r e c t i o n , metal d i s s o l u t i o n
is i n c r e a s i n g l y
hindered
by a process
which e v i d e n t l y
terminates
at
V
, a p o t e n t i a l of "complete p a s s i v i t y . "
Thereafter the HSssolution r a t e , i ,
sometimes orders
of
magnitude smaller than the p a s s i v a t i o n c u r r e n t , is independent
of p o t e n t i a l .
The
increase
in
current at some higher
p o t e n t i a l is determined by
the o v e r p o t e n t i a l of oxygen
discharge,
or the presence of some o x i d a t i o n - r e d u c t i o n
system. The region is termed " t r a n s p a s s i v e . "
The
term "Flade p o t e n t i a l , " V ,
has
a v a r i e t y of
connotations.
Many i n v e s t i g a t o r s , f o l l o w i n g Flade*s o r i g i n a l
d e f i n i t i o n , a s s i g n t h i s name to the p o t e n t i a l at which
an
already passivated metal begins
to l o s e passivity.(5-7) Some
p r e f e r to a s s i g n t h i s term to the p a s s i v a t i o n p o t e n t i a l V (8)
or to V
. (9) According to Tomashov and Charnova(4_) V^, i s t h e
thermodynamic p o t e n t i a l at which the formation
of a metal
oxide becomes p o s s i b l e and i t is lower than V , Figure 2.
As
much as p o s s i b l e the d i s c u s s i o n in t h i s pape? w i l l r e f e r to
P

6.
BRUSic
Ferrous
155
Passivation
Figure 1. A potentiostatic circuit: an imposed potential difference (V*) drives

the current (I) from an auxiliary electrode to the test electrode until the potential
difference (V) becomes equal to V *
PASSIVE
TRANSPASSIVE
'c
POTENTIAL
Figure 2.
A typical i - V curve on iron or steel

156
CORROSION
CHEMISTRY
the terminology given in this figure.

The definitions of the passive state are based on the
observation: a metal is passive when the amount of metal
consumed by a chemical or electrochemical reaction at a given
time is significantly less under conditions corresponding to a
higher a f f i n i t y of the reaction than under the conditions
corresponding to a lower a f f i n i t y (Wagner (10)), or, a metal
is in a state of
improved corrosion resistance (under
conditions where, from a thermodynamical point of view, the
metal is reactive) accounted for by inhibition of the anodic
process (Tomashov (5)). Such a definition enables us, without
hypothesizing about the nature of the oxidized state, to
distinguish between "the passivity" on one hand and
"the
inhibition" (and diminuation of the corrosion rate by paints
or galvanoplastie deposits) on the other. In the latter the
adsorption of the active species from the solution influences
the reaction kinetic
appreciably influencin
definition
differentiates clearly passivity
or
anodic
protection from the cathodic protection of a metal at low
potentials where metal is said to be "immune."
As seen from
Figure 3 the metal dissolution current in the passive region,
i , to be supplied for anodic protection is usually much
smaller than the cathodic protective current.
Also the
potential region is such that there can be no hydrogen
evolution (and metal embrittlement).
Figure 3 is a more
detailed version of Figure 2, indicating the location of the
corrosion potential and showing that i ^ (or ^
^ *
always the difference between i
and i
measure
ox
red.
Similar curves can be given to i l l u s t r a t e some practical
aspects of iron passivation:
iron can be passivated by concentrated but not dilute
nitric
acid (Figure
4), i.e., iron can
spontaneously
passivate.
i f corroding
in
an
electrolyte under
complete
diffusion control an increase of the electrolyte velocity may
passivate the iron. The smaller the pasivation current, the
easier the passivation (Figure 5).
coupling with Pt may involve passivity on T i (Figure
6) but not on iron (Figure 7) as long as i t s active-passive
transition
range
l i e s above
the
reversible hydrogen
potential.
Both theoretically and practically, however, the most
interesting aspect of the passivation phenomenon is seeking
the mechanism underlying the enforced passivation, the search
for the "cause" of passivation and f u l l e r understanding of the
surface changes resulting in active-passive transition.
s
m e a s u r e (

6.
Ferrous
BRUsic
Passivation
Figure 3.
Effect of applied anodic and cathodic currents on the behavior of an

active-passive system
Figure 4.
Effect of oxidizer concentration on the electrochemical behavior of an

active-passive metal

157
158
log i
Figure 5.
Effect of velocity on the electrochemical behavior of an active-passive

metal under diffusion control
log i
Figure 6.
Spontaneous passivation of titanium by galvanically coupling to phtinum

6.
BRUsic
Ferrous
Passivation
159
B. P a s s i v a t i o n T h e o r i e s , Iron e t a l . The f i r s t theory of

p a s s i v i t y was
suggested over a century ago when Faraday (2)
s t a t e d "my strong impression is t h a t the s u r f a c e is o x i d i z e d
However, the i n v e s t i g a t i o n of the nature of
the
" p a s s i v a t i n g m a t e r i a l " introduced the t r a d i t i o n a l
polemics
between those supporting the a d s o r p t i o n theory and
those
supporting the o x i d e - f i l m theory of p a s s i v i t y .
The
controversy is at l e a s t p a r t l y due
to
semantic
ambiguities in the d e s c r i p t i o n of p a s s i v a t i n g f i l m s .
The
terms
most o f t e n
used
are
the f o l l o w i n g :
adsorbed
(chemisorbed)
oxygen and
oxygen-containing
species,(12)
monomolecular oxide,(13) monolayer (or l e s s ) of oxide,(14-20)
ordered, monomolecular, two-dimensional
f i l m of a
definite
chemical phase,(21) three-dimensional f i l m (22,23) oxid
t
r e l a t e d to any known
and duplex oxide.(26-29
alway
by " s u r f a c e o x i d e s " or " s u r f a c e a d s o r p t i o n , " e s p e c i a l l y when
coverage with oxygen is l e s s than a monolayer. In the o p i n i o n
of t h i s author the term
"adsorbed l a y e r " should be reserved
f o r the s i t u a t i o n shown in F i g u r e 8a, c h a r a c t e r i z e d by the
formation of p r e f e r e n t i a l l y u n i d i r e c t i o n a l bonding
between
adsorbate (oxygen) and s u b s t r a t e (metal) without
metal ions
leaving their l a t t i c e s i t e .
11
In c o n t r a s t , i t is suggested
that in the monomolecular
(or l e s s ) oxide l a y e r , metal atoms have l e f t
their regular
p o s i t i o n in the l a t t i c e (at k i n k s i t e s and any other s i t e s ) to
enter together with oxygen atoms i n t o a new,
alternating
arrangement
of
oxygen
and
metal,
which,
even
if
two-dimensional, resembles the arrangement in the formation of
the n u c l e i of the r e s p e c t i v e oxides ( i . e . ,
l a t e r a l bonds are
formed, F i g u r e 8b.(30)
In the three-dimensional oxide there is a
repeated
d i s t a n c e and symmetry r e l a t i o n s h i p in a v e r t i c a l
dimension
a l s o , with e i t h e r a more or l e s s continuous r e l a t i o n s h i p with
the s u b s t r a t e (as in e p i t a x i a l f i l m ) or with a complete
m i s o r i e n t a t i o n , as in n o n e p i t a x i a l , deposited f i l m .
There are a l s o s c i e n t i f i c d i f f i c u l t i e s in approaching the
problem of the e n t i t i e s formed in p a s s i v a t i o n .
T h i s is
p a r t i c u l a r l y so in the r e g i o n of low e l e c t r o d e coverage, where
there is no p o s s i b i l i t y of c l e a r l y d i s t i n g u i s h i n g between the
adsorbed or
(monomolecular or l e s s ) oxide l a y e r without
an
experimental method
that is s u f f i c i e n t l y
sensitive
and
a p p l i c a b l e in s i t u .
Experimental approach to the problem was
for
a long
time connected
with
the measurement
of
e l e c t r o c h e m i c a l parameters, which u s u a l l y measured an average
current d e n s i t y and thus gave l i t t l e
i n f o r m a t i o n about
the
l o c a l current d i s t r i b u t i o n , the nature and t h i c k n e s s of the
p a s s i v e f i l m , and the f i l m d i s t r i b u t i o n over the s u r f a c e . An

160
log i
Figure^ 7.
Increased corrosion rate of iron galvanically coupled with platinum in

air-free acid solution
-M-O-M-O-M-0-
'
-M-M-M-M-M-M1
Figure 8.
1*1
b)
-0-M-O-M-O-M-
0-M-O-M
c)
-M-M-M-M-M
I I I I I
-M-O-M-O-M-0I
-M-M-M-M-M-M-
-M-M-M-M-M-M-
Characterization of passivating films; (a) adsorbed layer, (b) monomolecular (or less) oxide, and (c) three-dimensional oxide

6.
Ferrous
BRUsic
161
Passivation
a p p l i c a t i o n of non-electrochemical methods on the other hand

may e i t h e r d i s t u r b the system under t e s t ( e l . d i f f r a c t i o n ,
microscopy,
Mossbauer) or be
complicated in i n t e r p r e t a t i o n
( e l l i p s o m e t r y ) . Some other d i f f i c u l t i e s i n v o l v e d in t h i s type
of experiment i n c l u d e a poor c h a r a c t e r i z a t i o n of the s u r f a c e ,
i t s pretreatment, c r y s t a l l o g r a p h i c
o r i e n t a t i o n and topography
... and the f a c t that in the r e g i o n of i n t e r e s t more than one
r e a c t i o n occurs simultaneously and
the k i n e t i c s parameters of
i n d i v i d u a l r e a c t i o n s are d i f f i c u l t to f o l l o w .
A l l these
f a c t o r s c o n t r i b u t e d somewhat to i n t e r p r e t i n g
the p a s s i v a t i o n
of metals
in
terms of a v a r i e t y of t h e o r e t i c a l models.
1. The Adsorption Theory.
The
adsorption theory
has
been developed by U h l i g ,
Frumkin, Kabanov and K o l o t y r k i n .
According to K o l o t y r k i n , (31) p a s s i v i t y is d e s c r i b e d as a
s p e c i f i c case of the widespread
phenomenon of the change in
the k i n e t i c s of an e l e c t r o d i
a d s o r p t i o n of the oxyge
g e n e r a l l y represented by
F
i = k
exp (-gj-) V ,
(3)
f
l C
where is the t r a n s f e r c o e f f i c i e n t
equal to $z;* when the
valency of the d i s s o l v i n g i o n , z, is u n i t y , is equal to the
symmetry f a c t o r
3,
or to the f r a c t i o n of the
potential
a v a i l a b l e to lower the energy
barrier for dissolution.
The
q u a n t i t y c is the number of atoms per square centimeter, and
i f w i t h the superimposition of a d s o r p t i o n , c' changes w i t h
p o t e n t i a l in such a way that
f
c' = c '
exp
F
(- - 5 7 )
(4)
the t o t a l current becomes

(a
i
= k
f
l C
exp
- a)F
RT
1
(5)
P r o v i d i n g that in the f i r s t stage of the p a s s i v a t i o n process

(at V < V < V )
a a and in the second
stage (at V > V )
2
1'
equation can e x p l a i n the experimentally observld
drop of the current with p o t e n t i a l and i t s independence of
p o t e n t i a l in the p a s s i v e r e g i o n .
The b a s i c anodic processes,
even in the p a s s i v e p o t e n t i a l r e g i o n , are d i r e c t d i s s o l u t i o n
of the metal
as one and the competitive adsorption of anions
2

162
as another.
In U h l i g ' s e a r l i e r view, one of the f a c t o r s determining
passivation
(and chemisorption) is the r a t i o of the work
f u n c t i o n to the enthalpy of s u b l i m a t i o n . I f t h i s r a t i o is
less
than u n i t y , c o n d i t i o n s are f a v o r a f l e to p a s s i v a t i o n
because the e l e c t r o n would escape more r e a d i l y than the atom,
f a v o r i n g the chemisorption of substances
like
oxygen.
A
p a s s i v e f i l m is composed, then, from chemisorbed
atomic and
molecular oxygen
(supplemented perhaps by OH and H~0). The
formation of chemical bonds s a t i s f i e s the s u r f a c e a f f i n i t i e s
of the metal without metal atoms l e a v i n g t h e i r l a t t i c e s i t e .
I t is argued (12) that on t y p i c a l t r a n s i t i o n metals (Ni,
W, Cr, T i , Ta) the formation o f such a l a y e r
( i . e . , M-0-0 )
proceeds with more f a v o r a b l e f r e e energy of formation than tne
oxide formation, as they have u n f i l l e d d e l e c t r o n
energy
levels
l e a d i n g t o th
between oxygen and th
typically exhibit passivity
f i l l e d d levels,
such as copper or z i n c , the heats of oxygen
adsorption a r e expected
t o be lower, and the formation of
oxides is l e s s
favorable.
Such
metals do not e x h i b i t
thin-film passivity.
C o r r e l a t i o n of the observed onset of Wagner's p a s s i v i t y
on a l l o y s l i k e Ni-Cu, Ni-Zn-Cu, and Cu-Ni-Al to the occupancy
of the d l e v e l s
of the a l l o y s is given in support of the
theory. According to the theory, the same type of p a s s i v e
film
( i . e . , M-O-O^) is formed in s o l u t i o n s , i n t e r p o s i n g a
s t a b l e b a r r i e r between metal and e l e c t r o l y t e ,
displacing
adsorbed
HÔ and i n c r e a s i n g the a c t i v a t i o n energy f o r the
h y d r a t i o n and d i s s o l u t i o n of the metal l a t t i c e .
Such f i l m s
are assumed t o decrease the exchange-current d e n s i t y
i ^ and
thus to i n c r e a s e the p o l a r i z a t i o n of the metal in the noble
d i r e c t i o n , where more oxygen can be adsorbed, which in turn
forms n u c l e a t i o n of metal oxides. Thus in the p a s s i v e s t a t e a
t h i c k e r oxide f i l m may be detected.
B r i e f l y , the theory e x p l a i n s the onset of p a s s i v i t y by
the formation of a t h i n adsorbed
l a y e r that e i t h e r s h i f t s the
e l e c t r o d e p o t e n t i a l in the double
l a y e r or i n f l u e n c e s the
k i n e t i c s of the anodic process; that is, the important
happenings occur in the s m a l l i n t e r f a c e r e g i o n between the
metal and the s o l u t i o n .
K o l o t y r k i n s theory, however, does
not d e f i n e a p h y s i c a l reason f o r the change of a s with
p o t e n t i a l . On the other hand, a chemisorbed f i l m of M-0-0
composition in the e l e c t r o l y t e is not very l i k e l y f o r the
f o l l o w i n g reason: Most metals (Cr, (32) T i , (32) Fe,(28,33)
N i , (34)) can be p a s s i v a t e d in a s o l u t i o n saturated with
deoxygenated argon - that is, with water oxygen - as long as
some water is present in the s o l u t i o n ; ( 3 4 ) in such s o l u t i o n s ,
2

6.
BRUsic
Ferrous
163
Passivation
the formation of molecular oxygen at low cathodic p o t e n t i a l s

is impossible,
and without i t s presence the toal number o f
millicoulombs determine^ in the f i l m
(0.01 C/cm according t o
U h l i g , or 1 t o 2 mC/cm
according t o Nagayama and Cohen(28)
and Brusic(33) at V ) and r e c a l c u l a t e d i n t o f i l m thickness
would exceed reasonaESe l i m i t s f o r the adsorbed monolayer of
oxygen i o n s . In the usual c o r r e l a t i o n between the number oJJ
millicoulombs and f i l m thickness i t i s assumed that 0.5 mC/cm
corresponds t o the monolayer of 0
ions
i f each metal i o n
adsorbs one oxygen i o n . I f the adsorbed l a y e r has a s t r u c t u r e
that contains
both metal and oxygen ions (as suggested more
r e c e n t l y by U h l i g (JL2) and by Garner and MacRae(35) f o r oxygen
adsorption and e q u a l l y
f o r the formation of the i n i t i a l f i l m
formed with the adsorption
of water,(36) the r e s u l t i n g
p a s s i v a t i n g f i l m is s e v e r a l l a y e r s t h i c k - that is, a t ^ i n
oxide is more l i k e l
Finally,
f a c t o r s tha
formation of oxides.
2
2.
The Oxide-Film Theory.
The
oxide-film
theory
d e s c r i b e s the s t a t e of improved c o r r o s i o n r e s i s t a n c e through
the formation
o f a p r o t e c t i v e f i l m on the metal substrate;
t h i s c o n s i s t s of the r e a c t i o n products of the metal with i t s
environment. Such a f i l m is a new phase, even i f i t is as
t h i n as a s i n g l e monolayer.(21) E l e c t r o n d i f f r a c t i o n (21) and
ellipsometric(33) studies
give the experimental evidence f o r
the theory.
In t h i s case the physicochemical p r o p e r t i e s of
the metal r e l a t i v e to a c o r r o s i v e medium depend to a l a r g e
degree on the p r o p e r t i e s
of
the p r o t e c t i v e f i l m .
The
p r o p e r t i e s of the f i l m , however, are not uniquely determined.
Adherents t o t h i s
theory have d i f f e r e n t opinions
on the
p o t e n t i a l at which the f i l m
forms, i t s t h i c k n e s s , the
mechanism of formation, and, most important, the "cause" of
passivity.
In the e a r l i e r t h e o r i e s i t was postulated that the
p a s s i v a t i o n follows the formation of a "primary l a y e r " o f
s m a l l c o n d u c t i v i t y , with porous c h a r a c t e r , which is sometimes
due
to
p r e c i p i t a t i o n of metal
salt
on and
near the
electrode.(32)
In the pores the current
i n c r e a s e s , and by
p o l a r i z a t i o n at an "Umschlagspotential"
( V = V , Figure 1) an
a c t u a l passive l a y e r is formed. Thus the e s s e n t i a l concept of
the p a s s i v a t i o n process is connected with the change of the
p r o p e r t i e s (chemical
or p h y s i c a l )
of the primary f i l m at a
certain potential.
The passive f i l m is f r e e from pores and
presents a b a r r i e r between the metal and the environment. I t
is
electronically
conductive and
slowly
corrodes
in
solution.(6,8,24,37)
These general ideas were f u r t h e r developed in d e t a i l by
Sato and Okamoto,(38,39) and B o c k r i s , Reddy, and Rao.(40) Sato
F

164
CORROSION
CHEMISTRY
and Okamoto have s t u d i e d the i - V curve f o r n i c k e l in a c i d

s o l u t i o n and have c a l c u l a t e d the p a s s i v a t i o n p o t e n t i a l as a
potential for
NiO/Ni^
transition.
T h i s was
in
fair
agreement with the experimentally observed v a l u e . The higher
valence oxide was thought to have a s e l f - r e p a i r i n g a b i l i t y ;
that
is,
a higher valence oxide theory of p a s s i v i t y
was
suggested.
In c o n t r a s t to t h i s higher valence oxide f i l m , a
s u r f a c e oxide f i l m NiO has
the same valency as the ions of
a c t i v e d i s s o l u t i o n ; thus i t has no s e l f - r e p a i r i n g a b i l i t y and
cannot p a s s i v a t e the metal.
Because anodic d i s s o l u t i o n s at
a c t i v e p o t e n t i a l s proceed at a high r a t e , Sato and Okamoto
have
suggested
that
the primary
film
forms
by
a
dissolution-precipitation
mechanism, although
no
direct
experimental evidence was
offered.
B o c k r i s , Reddy, and
Rao(40) have s t u d i e d the p a s s i v a t i o n of n i c k e l
in
acid
s o l u t i o n by a combinatio
situ
ellipsometry.
I
relatively thick
(6 X),
y
precipitation,
p o o r l y conducting, and is transformed i n t o well-conducting,
n o n s t o i c h i o m e t r i c NiO.
This transformation is thought
to be
the e s s e n t i a l step in the p a s s i v a t i o n process.
This theory, however, is not g e n e r a l l y accepted.
To
s t a r t with there is experimental evidence i n d i c a t i n g a l o s s of
c o n d u c t i v i t y and the appearance of the more ordered s t r u c t u r e
in the p a s s i v a t i n g n i c k e l oxide.(41)
A l s o , as pointed out by
Hoar,(14) some of the best p a s s i v a t i n g f i l m s ,
as those
on
aluminum or tantalum, are poor e l e c t r o n conductors, whereas
many p o o r l y p a s s i v a t i n g f i l m s ,
such as CuO or Pb0 , are
e x c e l l e n t e l e c t r o n conductors. A l s o , i t may very w e l l be that
the experimental r e s u l t s , in p a r t i c u l a r
the
ellipsometric
data
of B o c k r i s , et a l . , are in e r r o r due
to the p o s s i b l e
i n f l u e n c e of the continuous e l e c t r o d e roughening in the a c t i v e
p o t e n t i a l r e g i o n (see, f o r example, Refs. 33 and 42). Such an
e r r o r may be the reason that the reported r e f r a c t i o n index f o r
the f i r s t p a s s i v a t i n g f i l m is unusually high (about 4.0), that
the changes of e l l i p s o m e t r i c and
coulometric data in the
p a s s i v e p o t e n t i a l r e g i o n are not c o n s i s t e n t , and that the main
indicator
of
the
prepassive-film
transition
into
e l e c t r o n i c a l l y conducting f i l m is not trustworthy. The l a t t e r
was
d e r i v e d from the v a r i a t i o n of the
ellipsometrically
determined
change of
the
extinction
coefficient
with
potential.
9
De Gromoboy and
Shreir(43) argued in t h e i r experimental
study of n i c k e l in s u l f u r i c a c i d that higher oxides may form
d i r e c t l y from the metal and at the metal s u r f a c e ; the observed
"passivation potentials"
(determined
from anodic charging
curves) were found
to correspond c l o s e l y with the p o t e n t i a l s
calculated
for
N i + NiO,
N i ^ N i 0^,
Ni
Ni 0 ,
and

6.
Ferrous
BRusic
Passivation
165
Ni ->Ni0 , the phenomenon being sharply dependent

on the
presence or absence
of s m a l l c o n c e n t r a t i o n s of
thiourea.
S i m i l a r l y Arnold and Vetter(15) suggest the d i r e c t formation
of
NiO at the e l e c t r o d e .
From the anodic charging curves
these authors have
concluded that
the f i l m
reaches a
monomolecular
dimension
at
the
p o t e n t i a l of
complete
passivity.
T h i s and many other s i m i l a r hypotheses
can be s a i d to
form the
monolayer-oxide
theories.
Here the
onset of
p a s s i v i t y is due to the formation of a s i n g l e phase, an oxide,
which is very t h i n in t h i s p o t e n t i a l r e g i o n (at V , < 1) and
grows to a monolayer at V
.(13-18,44,45) I t s formation is a
potential-dependent reactiBR i n v o l v i n g the d i r e c t o x i d a t i o n of
the
metal by
the
discharge
of water,
which,
once
thermodynamically p o s s i b l e , is suggested to be
kinetically
easier
in
its
c r u c i a l primary
stage
than
is
metal
d i s s o l u t i o n . However
simultaneous e l e c t r o d
current is described as a r e s u l t
of a decrease in f i l m - f r e e
area or b l o c k i n g of the most a c t i v e , k i n k , s i t e s ( 4 4 ) caused by
f i l m formation and i t s i n f l u e n c e on the k i n e t i c s of the anodic
reaction.
In
t h i s respect and regarding the d i s c u s s i o n on the
i n i t i a l p a s s i v a t i o n s , as pointed out by an i n c r e a s i n g number
of
w r i t e r s , the o x i d e - f i l m and a d s o r p t i o n t h e o r i e s do not
c o n t r a d i c t but r a t h e r supplement one another. In l o o k i n g at
the primary act of p a s s i v a t i o n as the formation of a t i g h t l y
h e l d monolayer c o n t a i n i n g oxide or hydroxide anions and metal
cations.
Hoar(14) concurs with " a d s o r p t i o n i s t " U h l i g
and
Frankenthal as w e l l as " f i l m i s t s " Schwabe and A r n o l d , V e t t e r
and Evans.
In the formation of such a f i l m , a d s o r p t i o n may,
however, play an important r o l e . ( 4 6 )
Adsorption is the f i r s t
stage of the process; in an oxygen atmosphere molecular oxygen
is adsorbed, d i s s o c i a t e d , and chemisorbed, whereas in an
aqueous s o l u t i o n water molecules or OH w i l l be adsorbed and
chemisorbed
(see Figure 8a).
The
second
stage is the
i n t r u s i o n of metal ions from the l a t t i c e i n t o
the adsorbed
l a y e r (see F i g u r e 8b), which in the t h i r d stage may
grow in
the t h i r d
dimension. With
time and p o t e n t i a l (at V >
V )
oxide growth is a f u n c t i o n of the f i l m ' s i o n i c and e l e c t r o n i c
c o n d u c t i v i t y . The thickness of the f i l m w i l l then be f u r t h e r
r e s p o n s i b l e f o r the r e t a r d a t i o n of the anodic processes, both
growth of the oxide and anodic d i s s o l u t i o n , s i n c e the ions
have to pass through the p r o t e c t i v e f i l m . Thus one may speak
of a combined o x i d e - f i l m - a d s o r p t i o n theory of p a s s i v i t y . ( 5 )
2

166
CORROSION
CHEMISTRY
C h a r a c t e r i z a t i o n of A c t i v e and Passive State

A) Thermodynamics of the A c t i v e - P a s s i v e T r a n s i t i o n
If faced with the task of d e c i d i n g whether a p a r t i c u l a r metal
would be s u i t a b l e as a f a b r i c a t i o n m a t e r i a l in a given
environment, one l i k e s to know a) what kinds of spontaneously
o c c u r r i n g r e a c t i o n s are expected and b) what is the magnitude
of the r a t e of metal d i s s o l u t i o n .
The l a t t e r is the r e a l
c r i t e r i o n in making the d e c i s i o n and is u s u a l l y
evaluated
through
experimentation.
The former provides a yes or no
answer regarding the s t a b i l i t y of the metal
and f a l l s w i t h i n
the scope of e q u i l i b r i u m thermodynamics.
The f a c t o r s
that determine whether an anode in aqueous
s o l u t i o n is a c t i v e , p a s s i v e , or b r i g h t e n i n g are (a) the
m e t a l - s o l u t i o n p o t e n t i a l d i f f e r e n c e and
pH and (b) the
anion/water r a t i o .
1. The M e t a l - S o l u t i o
metal-solution
potentia
i n f l u e n c e of
pH, determines
whether the
formation of
aquocations
or oxide formation
is
the thermodynamically
prevailing possibility.
Such thermodynamic data, even i f
unsupplemented by i n f o r m a t i o n of
a k i n e t i c nature, are
usefully
expressed
in
the g r a p h i c a l
form devised
by
Pourbaix.(11) The Pourbaix diagram f o r i r o n is shown in F i g u r e
9.
Here, f o r example, one can make use of the r e l a t i o n
between free-energy change and e q u i l i b r i u m p o t e n t i a l to o b t a i n
f r e e energy
changes f o r p o s s i b l e c o r r o s i o n ,
i.e., iron
d i s s o l u t i o n caused by the hydrogen e v o l u t i o n r e a c t i o n : as the
sum
of the two f r e e energy
changes y i e l d s
the t o t a l
free
energy change f o r the c o r r o s i o n process
G = -nFV
(6)
a diagram i n d i c a t e s
that i r o n in deaerated
aqueous s o l u t i o n s
w i l l have a tendency to d i s s o l v e as long as the pH is l e s s
than about 8.5. In order that oxide formation may proceed,
the anode p o t e n t i a l must be at l e a s t as high as that f o r oxide
or
hydroxide
formation from
the metal
and water in the
particular solution.
I f the oxide forms as a "monolayer," there is a question
as to whether or not one can apply with some assurance these
thermodynamic data, obtained on
the bulk oxides.
Some
experimental evidence does i n d i c a t e that f o r many metal-oxide
systems the f r e e energy of formation of the f i r s t monolayer is
indeed
c l o s e to that observed
f o r the bulk phase,(47) and
hence no a p p r e c i a b l e d i f f e r e n c e in the r e v e r s i b l e p o t e n t i a l
should be expected.
On the other hand, Vermilyea(48) has
shown t h a t , i f the f i r s t
monolayer forms by two-dimensional
nucleation,
the
p o t e n t i a l of
the
two-dimensional-film
formation may be lower than that expected from the

6.
BRusic
Ferrous
Passivation

167
168
CORROSION
CHEMISTRY
thermodynamics, the actual potential being dependent on the

relative
values for
the
i n t e r f a c i a l energies
between
metal-film, film-solution, and metal-solution.
2.
The Anion/Water Ratio.
The second factor is
Hoar s ( 1 4 )
extension
of the
Pourbaix
diagram,
shown
schematically
in
Figure 1 0 .
It illustrates
the joint
influence
of the
measurable anode
potential and
the
anion/water ratio, when the anions, such as halides, interact
with oxide causing i t s breakdown. At a low c^-/c^
ratio the
electrode may behave according to the appropriafce Pourbaix
diagram, showing regions of active, passive (sometimes having
more than
one oxide with passivating properties), and
transpassive behavior.
At higher
X""/ H 0
^
^
electrode brightens (proces 7 )
higher potentials (proces
ion adsorption on metals and oxides are very scarce, the
diagram should be taken only as a qualitative display of
experimental results.
Thermodynamic data can, of course, give only information
on what is possible, without t e l l i n g us which oxide or
hydroxide is in fact most readily formed from a number of
possible candidates that may be thermodynamically stable under
a particular set of conditions, and without t e l l i n g us whether
any particular oxide is protective.
1
B) Experimental Approaches of Interest.

1)
Electrochemical.
Both galvanostatic and
potentiostatic
measurements have
been
very useful
in
characterizing passivation processes, in spite of the earlier
mentioned weaknesses in their application, especially since
they have been supplemented by other techniques, such as
potentiodynamic analysis, coulometry and ac-impedance(49-52)
investigation on either stationary or rotating electrodes.
They can indicate i f a metal undergoes an active-passive
transition under the given conditions, provide the rates and
mechanisms of relevant reactions,
give corrosion rates,
determine
the
presence
of
reaction
intermediates
(impedance(49)), evaluate electrode capacity, speculate on
oxide composition,
(28,29,44,45,53)
and detect i t s f i r s t
appearance(21) and
thickness.(28,44)
2)
Optical.
At least two methods should be
mentioned: ellipsometry and photopotential measurement. Both
can be applied in s i t u while the metal is a part of the
electrochemical
cell
and
under
an
electrochemical
investigation. Ellipsometry is based on the sensitivity with

6.
BRUsic
Ferrous
169
Passivation
4|K
PASSIVE
2_
1
-*T
ACTIVE
C
_ / C
H 0
2
Corrosion Science
Figure 10. Scheme showing anode behavior at various potentials in solutions of
various anion/water concentration ratios CX-/CH OThe processes are as follows:
(1) anodic passivation; () activationthe Flade relation; (2) activation by adding
"corrosive" anions; (3) transpassivation by raising the anode potential; (3') repassivation by lowering the anode potential; (4) breakdown via pitting, leading to
anodic brightening by raising the anode potential; (4') repassivation by lowering
the anode potential; (5) breakdown via pitting, leading to anodic brightening by
adding "corrosive" anions; (5') repassivation by removing "corrosive" anions; (6)
anodic brightening by raising the anode potential in concentrated solution; (6')
anodic etching of brightening metal by lowering potential in concentrated solu
tion; (7) anodic brightening from etching by increasing the anion concentration;
(7 ) anodic etching from brightening by decreasing the anion concentration (14).
2

170
which p o l a r i z e d l i g h t f o l l o w s the v a r i a t i o n of surface s t a t e s

of a metal.
F i g u r e 11 gives a schematic r e p r e s e n t a t i o n of the
instrument.
Changes introduced by the p a s s i v a t i o n process are
measured as changes in the readings
of the p o l a r i z e r and
analyzer, and compared with the values f o r a bare substrate;
these in t u r n are used to c a l c u l a t e the thickness and
the
r e f r a c t i v e index
(composition ?) of the newly formed
film.
R e l a t i v e changes of l e s s than 1 X are d e t e c t a b l e .
The
e v a l u a t i o n of the absolute values, however, may
not
be
s t r a i g h t f o r w a r d i f the f i l m is absorbing and
i t s refractive
index unknown.
The
photopotential
data
are
measured by
a
pulse
technique, t h ^ d u r a t i o n of the l i g h t pulse being
0.2 - 1 10
seg and the r a t i o of l i g h t to dark time
1 - 2.5
10
.
The
o s c i l l o g r a p h i c r e c o r d i n g of
the
photopotentials
allow
th
determinatio
f
n-typ
semiconducting p r o p e r t i e
c o r r e l a t i o n between th
p h o t o p o t e n t i a l s i g n f o r given experimental
conditions
is
formulated by Rosenfeld et al.(41,54) as
2~
(hv)
7-
2e
&n J ^n-+r
[M
- C
(7)
where k is Boltzmann s constant,

temperature, and in square
brackets are the concentrations,
exceeding the stoichiometry,
of the r e s p e c t i v e i o n s .
P o s i t i v e photopotential indicates
hole c o n d u c t i v i t y .
Furthermore, the
specimen may
be t e s t e d
with l i g h t
of d i f f e r e n t wavelengths: thus i t is p o s s i b l e to
speculate
on
the
kind of surface product
through
the
approximate value of i t s p h o t o e l e c t r i c gap.(55)
3) Other Non-Electrochemical
Methods.
B. Cahan(56) is
examining the p a s s i v a t i o n of i r o n and f e r r o u s a l l o y s by
a
combination of electromodulation, e l l i p s o m e t r y , ESCA, LEED and
Auger spectroscopy coupled with
e l e c t r o c h e m i c a l methods.
The
novelty
of the __êchnique is a c e l l with
a t h i n l a y e r of
electrolyte
(10
cm)
which w i l l be f r o z e n during
sample
t r a n s p o r t a t i o n from the e l e c t r o c h e m i c a l set-up i n t o the Auger,
f o r example, and then sublimed under a very high vacuo.
In
t h i s way, the e r r o r s due to a i r exposure w i l l be, h o p e f u l l y ,
avoided.
Results are not yet a v a i l a b l e .
C) K i n e t i c s and Mechanism of Relevant Reactions Q u a n t i t a t i v e E v a l u a t i o n of the i-V Curve.
Iron
p a s s i v a t i o n has been widely s t u d i e d , e s p e c i a l l y in n e u t r a l
s o l u t i o n s both experimentally and t h e o r e t i c a l l y .

6.
BRUsic
Ferrous
Passivation
171
(28,42,45,50,57-59) Seeking to understand q u a l i t a t i v e l y and

quantitatively
the processes
responsible for a t y p i c a l
i-V
curve, two viewpoints w i l l be brought i n t o focus:
1) the work
of Brusic(33) and
Bockris et a l . , (60) which gives the f i r s t
d i r e c t e v a l u a t i o n of the growth mechanism of the f i l m on i r o n
in the a c t i v e p o t e n t i a l r e g i o n and 2) the work of Ebersbach,
Schwabe and Ritter(18,19)
c o n t a i n i n g the
f i r s t theory
that
succeeded in c a l c u l a t i n g an
i-V curve
( f o r n i c k e l ) in good
agreement with the experimental r e s u l t s .
1)
The Model of B r u s i c , B o c k r i s et a l .
T h i s model
assumes, as does that of others,(18,45) that in the a c t i v e
r e g i o n both f i l m formation and d i s s o l u t i o n r e a c t i o n s proceed
as simultaneous processes
Th
advantag
h e l d her
is tha
many of the unknown parameter
film-forming r e a c t i o n
experimentally
i r o n in borate b u f f e r . K i n e t i c parameters were evaluated by a
combination of e l e c t r o c h e m i c a l and
e l l i p s o m e t r i c measurement
in a p u r i f i e d , deaerated s o l u t i o n , with and without s t i r r i n g .
The
e l l i p s o m e t e r was
used as
a quasi-automatic
instrument,
recording
changes with
time as short as 0.01
sec.
The
e s s e n t i a l r e s u l t s are
F i l m growth commences l e s s
than 0.01
sec a f t e r
switching on the current or p o t e n t i a l . The growth r a t e is not
a f f e c t e d by s t i r r i n g . A f t e r the
f i r s t s e v e r a l seconds at any
one
time the
growth r a t e is independent of the p o t e n t i a l .
Ellipsometric
changes obtained
in
o x i d a t i o n and
subsequent
r e d u c t i o n are r e v e r s i b l e (Figure 12).
Change of e l l i p s o m e t r i c parameters with p o t e n t i a l show
two i n f l e c t i o n p o i n t s , one a s s o c i a t e d with V
and the other
with a higher, p a s s i v e p o t e n t i a l , Figure 13.
^
The number of millicoulombs obtained in f i l m r e d u c t i o n
is
always lower than the number spent in o x i d a t i o n
(iron
d i s s o l u t i o n , hydrogen o x i d a t i o n ) . For
e v a l u a t i o n of the f i l m
thickness
the r e d u c t i o n
charge was
used, c o r r e c t i n g f o r
hydrogen e v o l u t i o n (Figure 14).
The evaluated thickness at constant, a c t i v e , p o t e n t i a l
is l i n e a r l y p r o p o r t i o n a l to time up
to about o n e - t h i r d
of a
monolayer (up to ^ 0.1 s e c ) ; t h e r e a f t e r i t is p r o p o r t i o n a l to
log t (Figure 15).
The
most l i k e l y
oxide
composition
and
thickness
evaluated from both e l l i p s o m e t r i c and coulometric r e s u l t s are
given in Figure 16 as FeiOH)^ below V
and Fe20^ above i t .
The
suggested mechanism, w h i c h ^ y i e l d s
good agreement
( q u a l i t a t i v e and
q u a n t i t a t i v e ) with the observed r e s u l t s , is
as f o l l o w s :
1. D i s c r e t e centers
grow, i n i t i a l l y
two-dimensionally,
up to 30% coverage.

172
Figure 11. Schematic of ellipsometer: (1) source of light; (2) collimator; (3) pohrizer; (4) compensator; specimen (S) on table (T); (5) filter; (6) analyzer; (7) light
detector
TIMER, EACH MARK REPRESENTS 5 SECS

Figure 12. Laboratory record of potentiostatic oxidation at -\-860 mV (she) and
reduction with simultaneous recording of ellipsometric intensity (i.e., A) and
charge. Stirred solution.

6.
BRUSIC
Ferrous
173
Passivation
r
10
8-l7Â/cm
8
T 6
t 4
-~rt
-400
0
400
800
POTENTIAL [mV,SHE]
Figure 13. Variation of and with potential in steady state and transient (x,
0.8; 0, 0.32; , 0.08 mA cm' ) oxidation; and i-V relation in steady state oxidation.
(,) Galvanostatic oxidation transients; (UO) potentiostatic (steady state) oxi
dation.
2
Figure 14. Charge (Q) as a function of oxidation potential obtained during the
oxidation (O), reduction (X), and reduction corrected for hydrogen (A)

174
()
i
0
200
400
600
TIME (SEC)
(b)
800
1000
O"
1.0
~ 0.6
0.2
\y
\
0.02
0.06
I
0.14
I 1L
0.10
0.16
TIME (SEC)
(0
<5
_l
r
-2
I
0
LOG
Figure 15.
I
TIME
(a) Increase of film thickness with time; (b) during the initial state;
and (c) with log (t) at490 mV (she)

BRUsic
Ferrous
Passivation
-600 -400 -200
200 400
600
800
POTENTIAL [mV, SHE]

Figure 16.
The solution of the ellipsometric results using coulometry

176
CORROSION
CHEMISTRY
2. At higher coverages
the growth i n v o l v e s a r a p i d
place-exchange step w i t h a rate-determining Temkin discharge
of OH i n t o s i t e s where the metal is already attached to an OH
group.
This i n i t i a l
OH group is d i s p l a c e d i n t o the f i r s t
l a y e r of
metal
atoms beneath
the s u r f a c e ,
forming
a
two-dimensional oxide
lattice.
Thus
the processes
that
determine the i - V curve are
Fe + OH"
/
dissolution
FeOH
FeOH
+ e
FeOH + e~
\
f i l m formation
(9)
FeOH ^
(8)
HOFe
(10)
FeOH F e
(12)
where Eq. (9) gives i ^ g and Eq.
(12) i ^
. At any time i
i ^
+
The d i s s o l u t i o n mechanism is b a s i c a l l y that of
B o c f r i s et al.,(61) r e c e n t l y confirmed by Epelboin.(52)
Since, according t o the determined
mechanism of f i l m
growth i
f (V,L) at t = const and i ^ 0 at t l a r g e , the
experimental i - V curve is l a r g e l y
determined by
l a t t e r is c a l c u l a t e d
as a f u n c t i o n of i n c r e a s i n g f e ( 0 H )
coverage from 0 to about 0.8 at p o t e n t i a l s in the p r e p e a l
r e g i o n and in the regions of f i n a l covering of the e l e c t r o d e
by the formation of FeÔ^ at p o t e n t i a l s between V
and V .
The f i n a l r a t e s are as f o l l o w s :
at V < V :
1 S
îss
ff
l 0H~
2 FeOH
( V F / R T
F V
13
>
R T
< / )
< >
e x
<- (
) / )
0-
where is the e l e c t r o d e coverage with
f(6)
OH,ads
Fe(OH)
and
^ 3(const + FV)

6.
BRUSIC
at V
Ferrous
177
Passivation
< V < V
1PP
i
^(1
diss
- ) exp
(3FV/2RT)
(15)
and
i
= k K ( l - ) exp
(3FV/2RT)
(16)
with
(1 " 0 )
T
= A exp
[-k K
2
t]
(17)
The theory was foun

observed k i n e t i c s parameters such as the T a f e l slope of f r e e
d i s s o l u t i o n of 150 mV, d i f f / d V = 0, and the observed i-V curve.
Place exchange, in the formation of the f i r s t or second
l a y e r of the f i l m , may be r e l a t i v e l y r a p i d , helped by e x i s t i n g
d e f e c t s at the surface or by
the i n f l u e n c e of metal
image
f o r c e s on the a c t i v a t i o n energy f o r the step. At higher f i l m
thicknesses
(thus at higher p o t e n t i a l s ) p l a c e exchange
may
become a rate-determining step, or, in general, the mechanism
suggested f o r the prepassive p o t e n t i a l r e g i o n ceases to be
valid.
I f compared with other models of i r o n p a s s i v a t i o n the
present model, showing c l e a r l y
that an
ellipsometrically
d e t e c t a b l e phase is formed negative to the peak p o t e n t i a l with
an e f f e c t i v e thickness of one,
perhaps two, monolayers at V
is not in agreement with models f a v o r i n g the a d s o r p t i o n
0
, OH , e t c . I t is in agreement with a more general p i c t u r e
of
monomolecular
oxide formation, in p a r a l l e l
to
iron
dissolution(44)
directly
at
the e l e c t r o d e
surface,(14)
p o s s i b l y favored by the d-character of the s u b s t r a t e ( r a c t i o n
8).(12)
I t a l s o agrees with t h e o r i e s proposing the appearance of
a higher v a l e n t oxide at V > V . (58)
As
f o r the
film
composition in general, the
have more supporters
than
process.
I t remains
to be determined
by
more d i r e c t
experimental approaches(56) which of the two is more l i k e l y .
2
)
o l f Ebersbach,
Schwabe and
R i t t e r (18,19).
It was assumed that the m e t a l - d i s s o l u t i o n r e a c t i o n (rate i ^ )
and
the f i l m - f o r m i n g r e a c t i o n ( i ) at an i n i t i a l l y
bare
9

CORROSION
178
CHEMISTRY
e l e c t r o d e can proceed simultaneously with a p o s s i b i l i t y of the

f i l m s being d i s s o l v e d by the a c t i o n of the e l e c t r o l y t e ,
e s p e c i a l l y i f some adsorbable anions are present. Thus
1
i - ( i + i ) (1 - )
x
(18)
where , the e l e c t r o d e coverage, v a r i e s with time according to
= C i ( l - ) -
- ,
V,a _,a
A
(19)
H +
where B, the r a t e of oxide

c
according to
f i l m degradation, is a f u n c t i o n of
Ht
MO + 2 H
2 +
+ H0
(20)
and K, the r a t e of o x i d e - f i l m
according t o
MO + 2A~ + H 0
2
MA
degradation, is a
f u n c t i o n of
+ 20H~
(21)
Then
- ( i + i ) ( l - (1 + ^ g j - )
x
{1 - e x p [ - ( C i
+ + B)t]})
(22)
where
-*
- i exp
2
< "
V I
fc
H+
(V - V ) ] , i = f c
2
H +
'

(24)
6.
Ferrous
BRUSic
179
Passivation
with
and V being the e q u i l i b r i u m p o t e n t i a l s f o r a c t i v e
d i s s o l u t i o n and f i l m formation.
The d i s s o l u t i o n r a t e i ^ may be determined by the r e a c t i o n
sequence given by Eqs. 8,
9, and
11 ( B o c k r i s
dissolution
mechanism). The mechanism of f i l m formation, r e s u l t i n g in ^
is assumed to be as f o l l o w s :
1
M + H0
2
MOH
+ H0
2
M(OH)
MOH
+ H
+ e
M(OH) + H
2
MO + H 0
(25)
+ e"
(26)
(27)
with the second e l e c t r o n t r a n s f e r being r a t e determining.

The
mechanism i n v o l v e s the d i r e c t formation of the p a s s i v a t i n g
f i l m at the e l e c t r o d e s u r f a c e , experimentally supported
by
work on a r o t a t i n g n i c k e l d i s k electrode,(62) which i n d i c a t e s
that the r a t e of the p a s s i v a t i o n process is independent of
s t i r r i n g and of the s o l u b i l i t y of the n i c k e l s a l t .
For the steady s t a t e , t > ,
00
i- exp[(-F/RT)(V - V_)] + i exp[(a F/RT)(V - V ) ]

= -J:
i
i
_
1 + ({Ci
exp[(a F/RT)(V - V ) ] } / ( K + ))
9
(28)
and i f no o x i d e - f i l m degradation occurs,
h
i
(29)
exp ( i C t )
According to Eq. (19), the constant C is the covered area
per coulomb and was estimated on the b a s i s of the
area r e q u i r e d f o r oxygen atoms as 10^ cm^/A-sec.
The r a t e constants and
at constant pH
and
2

180
anion c o n c e n t r a t i o n were given as f i r s t - o r d e r

r a t e constants
with estimated v a l u e s _ o f
10
> (K +
B) > 10
sec
.
These l i m i t s
were chosen
arbitrarily,
assuming that f i l m degradation is slower
than
f i l m formation. C u r r e n t - p o t e n t i a l curves were c a l c u l a t e d f o r
a l a r g e v a r i a t i o n of parameters and
d i d indeed
show a
resemblance to the experimental r e s u l t s
(carried
out f o r
n i c k e l in a c i d ) .
Examples arg shown_^n Figures 17 and 18 f o r = 3 Z / $ - Z ^
= 2
(or 1), i
= 10
A/cm
(chosen a r ^ i t r a r i l y f r o m ghe
r e g i o n of_Yglues reported to be between 10
and 10
A/cm)^
i
=
(ggain a r b i t r a r i l y
assumed to vary between 10
and 10
A/cm , that is, in the same r e g i o n of values as the
d i s s o l u t i o n current i ^ ) .
These f i g u r e s show the v a r i a t i o n
in peak current or p e a i P p o t e n t i a l with both
time (Figure 17)
and
the v e l o c i t y
o
(Figure 18). Thus, accordin
w i l l be zero when = 1 at V
. Furthermore, according to Eq.
(29), in the s t a t i o n a r y s t a E l
(when t
) a f i n i t e current
can flow only when i
0.
I t is argued t h a t , in r e a l i t y , a
measurable current w i l l always flow a f t e r p a s s i v a t i o n even i f
2 ~* 0 because the s u r f a c e f i l m is not p e r f e c t nor is the
s u r f a c e p e r f e c t l y covered,
and that the p a s s i v e s u r f a c e f i l m
is not
a b s o l u t e l y impermeable.
Thus, as
polarization
i n c r e a s e s (at V > V ) , ions i n c r e a s i n g l y penetrate
i n t o the
film, increasing its ?hickness.
A l s o , the theory gives an acceptable model of a v a r i e t y
of p a s s i v a t i n g behaviors observed on d i f f e r e n t metals:
1) metals with
<< 0: the p a s s i v a t i o n r e a c t i o n
occurs
f a s t and
metal in aqueous s o l u t i o n always forms
an
oxide, as in the case of A l , T i , Zr, Ta, and W.
2) V - % 0: in that case the metal is i n i t i a l l y
a c g i v e ^ the more negative (V^ - V^) and tjje smaller the r a t i o
1~ I2 >
f a s t e r the p a s s i v a t i o n a) i.. / i
> 1:
t h i s is
trie case f o r Fe,
Co and
N i in s o l u t i o n without
halides.
P a g s i v g t i o n is p o s s i b l e only at higher anodic p o t e n t i a l s ,
b)
i.. / i
1 p a s s i v a t i o n occurs e a s i l y , the case of Cr.
3) V - 0:
a)
i /
1, the case of Ag; the

p a s s i v a t i o n p o t e n t i a l is not
e a s i l y reachable even at high
anodic current d e n s i t i e s . P a s s i v a t i o n may set in a f t e r a s a l t
formagion^ e.g. Ag S0^ in whose pores A g 0
can be formed,
b) i ^ / i
<< 1 - metals of the Pt group with slow d i s s o l u t i o n
and e a s i e r p a s s i v a t i o n .
Thus t h i s
theory s a t i s f a c t o r i l y d e s c r i b e s the i - V curve
in the a c t i v e p o t e n t i a l r e g i o n , with a q u a l i t a t i v e d e s c r i p t i o n
of p o s s i b i l i t i e s
in
the passive p o t e n t i a l r e g i o n and
a
s e m i - q u a n t i t a t i v e explanation of the p a s s i v a t i o n behavior of a
v a r i e t y of metals.
2
1 0

6.
BRUsic
Ferrous
181
Passivation
TIME
-250 0
250 500 750

POTENTIAL [mV SHE]
Electrochimica Acta
Figure 17.
Effect of time on the current density-potential curves by potentiostatic measurements (calculated for + = 10~ sec' (18))
3
K+B
-250
250 500 750

POTENTIAL [mV, SHE]
Electrochimica Acta
Figure 18.
Current density-potential curves calculated for t = oo showing de

pendence on the sum of the constants and (18)

182
CORROSION
CHEMISTRY
Final Remarks
Modern passivation theory views the primary passivation
act as a formation of a tightly held layer of monomolecular
dimensions, containing oxide or hydroxide anions and metal
cations; the process involves the formation of a new phase, an
oxide, in steps that include the adsorption as an important
intermediate stage. Thus the long-time controversial aspects
of the adsorption and oxide theories are, in one sense,
combined.
The observed current-potential behavior is a function of
the simultaneous processes of film formation, i t s dissolution,
and metal dissolution.
The latter
seems to be mostly
responsible for
the magnitude of
the current at a l l
potentials.
In the active potential region dissolution is
hindered by a decreas in th
fre electrod
d in th
passive region dissolutio
of the passivating film
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6.
Ferrous
BRUSIC
183
Passivation
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184
(47)
(48)
(49)
(50)
(51)
(52)
(53)
(54)
(55)
(56)
(57)
(58)
(59)
(60)
(61)
(62)
Brennan, D.,
Hayward, D. O. and T r a p n e l l , B. M.
W.,
Proc. Royal Soc. (London), A256, 81 (1960).
Vermilyea, D. ., in Advances in E l e c t r o c h e m i s t r y
and
E l e c t r o c h e m i c a l Engineering (P. Delahay,
ed.) V o l . 3,
I n t e r s c i e n c e , New York, 1963.
Epelboin, I. and Keddam, M., J. Electrochem. Soc., 117,
1052 (1970).
E p e l b o i n , I . , Gabrielli, C., Keddam, M., Lestrade, J. C.
and Takenouti, H.,
J.
Electrochem. Soc. 119,
1632
(1972).
E p e l b o i n , I., Keddam, M.
and Takenouti, H., J. Appl.
Electrochem., 2, 71 (1972).
E p e l b o i n , I. and Keddam, ., Electrochem. Acta, 17, 177
(1972).
Pigeand, ., J. Electrochem. Soc., 122, 80 (1975).
Oshe, . K. and
(1969).
T r a b a n e l i , G., Zucchi, F. and
Brunoro, G.,
Thin S o l i d
F i l m s , 13, 131 (1972).
Cahan, B.,
Case Western Univ., Cleveland, Ohio, p r i v a t e
communication.
N o v o s e l s k i i , I. M., Andreev, I . N. and Khakimov, M. G.,
Elektrokhimiya, 7, 421 (1970).
M i l i g y , . ., Geana, D. and Lorenz, W. J., Electrochem.
Acta 20, 273 (1975).
Sato, N., Noda, T. and Kudo, ., E l e c t r o c h i m . Acta 19 471
(1974).
B o c k r i s , J. O'M., Genshaw, . ., B r u s i c , V. and Wroblow,
H., E l e c t r o c h i m . Acta 16, 1859 (1971).
Bockris,
J.
O'M.,
D r a z i c , D. and D e s p r i c , A.
R.,
Electrochim. Acta 4, 325 (1961).
Ebersbach, U., Schwabe, K.
and Konig, P., E l e c t r o c h i m .
Acta, 14, 773 (1969).
R E C E I V E D September 1, 1978.

7
Corrosion of Valve Metals
J. E. D R A L E Y
Argonne National Laboratory, Argonne, I L 60439
I had a little problem deciding what kind of t a l k

to give you. I concluded that it should not be a gene r a l survey of everythin
corrosion of valve
it should not contain j u s t one or two topics within
that subject--about which I could talk enough to give
you some depth--but a compromise between these two.
Secondly, I had to decide whether to t a l k t h e o r e t i c a l l y
or mathematically, on the one hand, or phenomenologica l l y on the other, and I have chosen the l a t t e r approach. My intent is to give you some perspective
about the way these materials corrode.
I have selected
some examples that I think are s u f f i c i e n t l y general and
i l l u s t r a t e the p r i n c i p l e s well enough to do t h i s . Many
of the s l i d e s are taken from our own work of some years
ago.
I t must be acknowledged that the unique corrosion
c h a r a c t e r i s t i c s of a number of the valve metals are not
i d e n t i f i e d , and behavior in a number of common environments is not addressed.
F i r s t of a l l , I have found the t i t l e valve metals
to be confusing f o r a number of people; f o r example,
someone asked i f they are the metals of which valves
are made. Let me give you a few guidelines. F i r s t ,
the valve metals form r e l a t i v e l y perfect oxide f i l m s .
That means they are r e l a t i v e l y perfect with respect to
protection against corrosion, which we s h a l l amplify
a little.
Secondly, they are r e l a t i v e l y perfect insofar as there is not much l o c a l breakdown or leakage
when they are anodized.
P a r t l y r e l a t e d to that there
are high f i e l d s in these oxides during the period of
growth--fields greater than about 10 volts/cm.
In the f i r s t figure, we see i l l u s t r a t e d a r e l a t i o n ship often drawn between the energy of the bond between
oxygen and the metal and the f i e l d required to produce
an anodic f i l m . In t h i s instance, the f i e l d is that
6
0-8412-0471-3/79/47-089-185$12.50/0

186
40
MO BOND ENERGY, eV
Figure 1.
Field required to sustain an ionic current density of 2 X JO" A cm'

for anodic oxides as function of metaV-oxide bond energy (1)
3

7.
DRALEY
Corrosion
of Valve
Metals
187
which corresponds
t o a g i v e n s m a l l c u r r e n t in a n o d i z i n g ,
or production of the oxide f i l m .
The f a c t o r s
respons i b l e f o r sound and p r o t e c t i v e f i l m s are not w e l l known.
I t is s t i l l a b i t o f a m y s t e r y w h y s o m e s y s t e m s
form
better films than others.
A number o f i n d i v i d u a l
princ i p l e s have been brought up.
P i l l i n g and Bedworth
y e a r s ago w r o t e t h a t i f t h e volume o f t h e o x i d e
prod u c e d o n a m e t a l s u r f a c e is l e s s t h a n t h e v o l u m e
of
m e t a l f r o m w h i c h i t is p r o d u c e d ,
t h e r e is l i t t l e
chance
t h a t t h e o x i d e f i l m w i l l be p r o t e c t i v e .
As s t a t e d ,
t h a t is a g o o d g u i d i n g p r i n c i p l e , b u t o f a l l t h e
syst e m s f o r w h i c h t h e r e is e x p a n s i o n in t h e f o r m a t i o n o f
oxide, the r u l e doesn t p r e d i c t r e l i a b l y which oxides
w i l l be p r o t e c t i v e and w h i c h w i l l
not.
Strong bonding between the oxide and the m e t a l
s u b s t r a t e seems t o be e s s e n t i a l t o t h e f o r m a t i o n o f
highly protective films
you can h o l d on t o .
The o t h e r s d o n t work v e r y w e l l .
There are a l o t of p e c u l i a r i t i e s ; for example,
in
s o m e c a s e s t h e o x y g e n d i s s o l v e s s i g n i f i c a n t l y in t h e
surface layers of the metal.
This doubtless
reduces
the e f f e c t i v e
s i z e o f the s u r f a c e m e t a l atoms and
allows adjustment of the p o s i t i o n s of the surface
atoms
o f t h e s u b s t r a t e so t h e y w i l l n e a r l y m a t c h the p o s i t i o n s o f t h e c o n t i g u o u s c a t i o n s in t h e
oxides.
F i g u r e 2 shows t h a t w h i c h m e t a l s f o r m g o o d f i l m s
depends not o n l y on the bond energy b u t a l s o on the
s o l u t i o n in w h i c h t h e f i l m s a r e f o r m e d .
These
curves
a r e f o r a n o d i z i n g a l u m i n u m in a s e r i e s o f
solutions.
The top 5 c u r v e s a r e f o r a f a m i l y o f s o l u t i o n s
in
which the f i l m s remain r e s i s t a n t to greater
thicknesses
t h a n f o r t h e two l e s s i d e a l s o l u t i o n s .
In other
solut i o n s , o n e c a n t g e t a n o d i z e d f i l m s at a l l .
The r e s i s t i v i t y o n t h e o r d i n a t e is f o r t h e f i l m i t s e l f .
I
t h i n k i t is i m p o r t a n t t o n o t e t h a t m a n y m e t a l s
form
h y d r a t e d o x i d e s , in w h i c h h y d r o x i d e i o n s a r e
constituents.
As a g e n e r a l r u l e , h i g h l y p r o t e c t i v e f i l m s are
a n h y d r o u s ; i t is o f t e n s p e c u l a t e d t h a t t h e h i g h f i e l d
present during the formation of the f i l m (vide
supra)
contributes to the formation of anhydrous r a t h e r than
the hydrated oxide.
I t is e a s y t o s e e t h a t a h i g h
f i e l d o p e r a t e s when one a n o d i z e s by t h e a p p l i c a t i o n o f
a p o t e n t i a l ; i t is l e s s o b v i o u s , b u t e v i d e n t l y e q u a l l y
true during unassisted thin-film oxidation.
Local
f i e l d s from m u l t i p l y - c h a r g e d cations might
contribute
to the formation of compact,
anhydrous oxides;
the best
films u s u a l l y contain cations w i t h a charge of 3 or
more.
One m o r e t h i n g a b o u t f i l m s :
they often are not
v e r y s t a b l e in w a t e r o r in a q u e o u s s o l u t i o n s .
This
tends to cause confusion about the p r o t e c t i v e n e s s
of
f

188
Barrier Film Thickness ( xlO )

2
100
15
12
(I) Sulphuric Acid

(2) Oxalic Acid
80
(4) Malonic Acid
(5) Chromic Acid
(6) Tartaric Acid
(7) Ammonium Borate
(IO%Solutions)
60
120
180
240
300
Quantity of Electricity (mQ/cm )

2
Electrochimica Acta
Figure 2.
Differential specific resistance for growing barrier films on aluminum

)

7.
DRALEY
Corrosion
of Valve
Metals
189
oxide films.
The f i l m i t s e l f may be a v e r y g o o d o n e ,
b u t i t may d e t e r i o r a t e , s o m e t i m e s s l o w l y ,
sometimes
r a p i d l y ; sometimes r a t h e r g e n e r a l l y and sometimes
locally.
I t s p r o t e c t i v e n e s s t h u s may b e t e m p o r a r y
or i m p e r f e c t as a f u n c t i o n of t i m e .
One o f t h e
conundrums about such p r o t e c t i v e f i l m s has always been
how t o r a t i o n a l i z e t h e d e m o n s t r a t e d r e q u i r e m e n t t o
a d s o r b s p e c i e s o n some m e t a l s u r f a c e s o r o n some m e t a l
oxide surfaces to provide p r o t e c t i o n .
I t appears
to
me t h a t t h e f u n c t i o n o f t h e a d s o r b a t e is t o
protect
the oxide f i l m against the h y d r a t i n g or s o l v a t i n g
effect of the water.
T h e f i l m i t s e l f is g o o d e n o u g h ,
then, to provide p r o t e c t i o n .
I n F i g u r e 3 we s e e t h e r e l a t i o n s h i p b e t w e e n m e t a l oxide bond energy and the T a f e l s l o p e - - t h e r e l a t i o n s h i p
between p o t e n t i a l and l o g c u r r e n t d u r i n g oxide
film
formation.
It says
e r g y is h i g h e r , i t t a k e
g i v e n i n c r e a s e in c u r r e n t , w h i c h is t o s a y t h a t w h e n
t h e b o n d e n e r g y is h i g h e r i t is m o r e d i f f i c u l t t o p a s s
e x t r a c u r r e n t t h r o u g h a more p r o t e c t i v e
film.
C o r r o s i o n and o x i d a t i o n of v a l v e metals g e n e r a l l y
c o n s i s t both of the growth and degradation of
oxide
films.
I ' d l i k e to begin d i s c u s s i o n of the growth of
o x i d e f i l m s w i t h F i g u r e 4, t a k e n f r o m H a u f f e ( 3 ) .
In
t h i s c a s e i r o n is o x i d i z e d d i r e c t l y t o f e r r i c
oxide
in a n i t r i c - n i t r o u s a c i d s o l u t i o n .
The a u t h o r has
suggested the existence of concentration gradients
for cation l a t t i c e defects,
oxygen v a c a n c i e s ,
and
electrons.
D u r i n g t h e g r o w t h o f t h e f i l m , i t is p r o posed that e l e c t r o n s , c a t i o n s , and anions migrate.
A
l a r g e space charge v a r i a t i o n
is
proposed w i t h i n the
o x i d e f i l m a c a s e w h i c h was i g n o r e d f o r y e a r s by
p e o p l e who s t u d i e d o x i d a t i o n .
The r e s u l t a n t c o m b i n a t i o n
of f i e l d s from surface charges and from the space
charge
l e a d s t o n o e l e c t r i c a l f i e l d at t h e i n t e r f a c e
between
Z o n e s I a n d I I at w h i c h l o c a t i o n n e w o x i d e
is
proposed
to form.
O t h e r more c o m p l i c a t e d models have been d e v e l o p e d ; I h a v e c h o s e n t o show t h i s b e c a u s e o f i t s
generally applicable principles.
I n F i g u r e 5 we s e e t h a t s o m e t i m e s s e e m i n g l y
perfect
t h i n f i l m s are f a r from perfect.
T h i s is f o r a n a l u m i n u m a l l o y t h a t , f r o m some t e c h n i q u e s , w o u l d a p p e a r
to
carry a perfect film.
We s e e s o m e o f a s e r i e s
of
p l a t e l e t s g r o w i n g o u t in t h i s t r a n s m i s s i o n e l e c t r o n
micrograph t a k e n across an edge.
F i g u r e 6 shows a c a s e
in w h i c h o x i d e n u c l e i g r o w o n a m e t a l s u r f a c e .
This
o n e is f o r i r o n in l o w p r e s s u r e o x y g e n ; s i m i l a r r e s u l t s
have been observed f o r other m e t a l s .
If
we l o o k
at
this surface during oxidation,
we s e e
only a very
thin

190

7. D R A L E Y
Corrosion
of Valve
191
Metals
Surface Charge
Plenum Press
Figure 4. Schematic of the concentration of the free electrons and ionr-defect
positions in the homogeneously structured passive layer Fe O with space-charge
inversion (3)
2
Academic Press
Figure 5.
Oxide platelets viewed by electron silhouette on aluminum after corrosion for 30 hoursinsteamat540 C (4)

192
Maruzen Co., Ltd.

Figure 6.
Oxide nuclei on (111) iron foil after oxidation at 540C and 1.1 X 10~
Ton for 55 minutes (5)

7.
DRALEY
Corrosion
of
Valve
Metals
193
f i l m u n t i l n u c l e i show up at the same t i m e at many

p l a c e s o v e r the s u r f a c e .
These c r y s t a l s t h e n grow at
m e a s u r a b l e r a t e s . T h e i r o r i e n t a t i o n can be d e t e r m i n e d
and r e l a t e d t o the o r i e n t a t i o n o f the m e t a l s u b s t r a t e .
I d now l i k e t o show you some u n p u b l i s h e d c o l o r
p h o t o g r a p h s o f a s e r i e s o f i r o n samples w h i c h were
o x i d i z e d f o r t h r e e days in w a t e r at e l e v a t e d temperat u r e s . We've changed the p o t e n t i a l f o r o x i d a t i o n by
u s i n g d i f f e r e n t c o n c e n t r a t i o n s o f oxygen in w a t e r .
W i t h 290 ppm oxygen c o n c e n t r a t i o n at 260C., a h i g h l y
p e r f e c t f e r r i c o x i d e f i l m formed showing a l i t t l e t i n t
o f i n t e r f e r e n c e c o l o r t h a t is o f t e n v a l u a b l e f o r g i v i n g
some c l u e s .
The c o l o r i n d i c a t e s t h a t the t h i c k n e s s is
u n i f o r m o v e r a b i g enough a r e a t o d e v e l o p the i n t e r f e r ence c o l o r ; in a few m i n u t e s , w e ' l l see t h a t t h i c k n e s s e s
sometimes v a r y from g r a i t g r a i n
A t 35
a r e a s o f breakdown a r
some p h o t o g r a p h s o f sample
,
the same c o n d i t i o n s .
Y o u ' l l see t h a t f o r the same oxygen c o n c e n t r a t i o n s in the w a t e r the p r o t e c t i o n is n o t
as good. A g r e a t e r o x i d i z i n g p o t e n t i a l (oxygen c o n c e n t r a t i o n ) is r e q u i r e d f o r a h i g h l y p r o t e c t i v e f i l m as
the t e m p e r a t u r e is l o w e r e d ; the t r e n d c o n t i n u e s t o
at l e a s t as low as 100C ( t h i r d s l i d e ) at w h i c h tempera t u r e 540 ppm O2 p r o v i d e d an e x c e l l e n t f i l m ( & ) . To the
b e s t o f my knowledge, nobody has u s e d t h i s system t o
m a i n t a i n the p o t e n t i a l l y e x c e l l e n t aqueous c o r r o s i o n
r e s i s t a n c e o f i r o n . The n e x t s l i d e shows a range o f
i n t e r f e r e n c e c o l o r s f o r c o n t i g u o u s g r a i n s on a s p e c i men o f i r o n , under c o n d i t i o n s i d e n t i c a l t o t h o s e shown
earlier.
I f t h e r e is a d e f i c i e n c y o f o x y g e n i n s u f f i c i e n t oxygen t o p r o v i d e good p r o t e c t i o n s i z e a b l e p i t s
a r e formed in p u r e w a t e r . A l e s s o n f r o m t h i s is t h a t
p i t t i n g doesn't o c c u r o n l y in s t r o n g e l e c t r o l y t e s o r
selected electrolyte solutions.
I f the c o m p o s i t i o n o f the a l l o y is changed the
c o m p o s i t i o n o f the o x i d e changes, and i t is p o s s i b l e
t o make the o x i d e c o n s i d e r a b l y more p r o t e c t i v e on a
m e t a l l i k e i r o n . The n e x t s l i d e shows the e f f e c t o f
a l i t t l e b i t o f chromium. C r o l o y - 5 c o n t a i n s 5% c h r o mium and some molybdenum; you can see t h a t at 260C w i t h
35 ppm 0 c o r r o s i o n r e s i s t a n c e is s u b s t a n t i a l l y b e t t e r
t h a n t h a t o f i r o n . As shown in F i g u r e 7 the c o r r o s i o n
b e h a v i o r o f s u c h a l l o y s a l s o seems f a v o r a b l y i n f l u e n c e d
by h i g h oxygen c o n c e n t r a t i o n in w a t e r . I n F i g u r e 8 i t
is seen t h a t t h e r e is c o n s i d e r a b l e chromium e n r i c h m e n t
in the o x i d e f i l m s on o x i d i z e d i r o n - c h r o m i u m a l l o y s ;
e v i d e n t l y the g r e a t e r p r o t e c t i v e n e s s o f the f i l m s f o r
the chromium-bearing a l l o y s is r e l a t e d t o t h i s composition.
F i g u r e 9 shows t h a t the r a t i o o f oxygen t o
f

194
Corrosion
Figure 7.
Corrosion of Croloy 2 k steelinwater at 260C (6)

x

7. D R A L E Y
Corrosion
of Valve
Metals
CHEMICAL ANALYSIS
24 Cr
14 Cr
-o-
5Cr
20
40
60
SPUTTERING TIME , min

Figure 8.
Cr/Fe ratio as a function of distance from surface for four oxidized

ironchromium alloys (7). Ratios for alloys on right.
40
80
120
SPUTTERING TIME, min

Figure 9.
O/M ratio as a function of depth in oxideiniron and iron-chromium

alloys (7)

196
CORROSION
CHEMISTRY
m e t a l a l s o v a r i e s w i t h i n the f i l m .
That c o r r e s p o n d i n g
t o M 0 is shown. As one g e t s c l o s e r t o the m e t a l ,
shown by s u r f a c e a n a l y s i s a f t e r s p u t t e r i n g some materi a l o f f the s u r f a c e , the o x i d e is seen t o have l e s s
oxygen in i t . I t is a n o t h e r p e c u l a r i t y o f some o f
t h e s e systems t h a t in the t h i n f i l m r a n g e , the s t o i e h i ometry o f the o x i d e is n o t as e x p e c t e d .
As most o f you know, i f n i c k e l is added t o c h r o mium a l l o y s a s e r i e s o f s t a i n l e s s s t e e l s is p r o d u c e d
w i t h q u i t e good c o r r o s i o n r e s i s t a n c e . These a l l o y s
have a w i d e s p r e a d use; t h e s e days t h o s e w i t h composit i o n s c l o s e t o 18 Cr-8 N i are i n c r e a s i n g l y b e i n g u s e d
in many p r a c t i c a l a p p l i c a t i o n s . I guess I s h o u l d
warn you t h a t i f you l i s t e n e d t o Roger S t a e h l e you h e a r d
t h a t t h e r e a r e a number o f i n s t a n c e s when t h e y a l s o
crack unexpectedly a f t e r a p e r i o d of exposure.
So
t h e y a r e by no mean
n e v e r t h e l e s s , they o f f e
in the p e r f o r m a n c e o f low t o moderate c o s t m a t e r i a l s .
F i g u r e 10 is made up t o show t h a t i f aluminum is added
t o 304 s t a i n l e s s s t e e l - - t h a t is r o u g h l y the s i m p l e 18
and 8 s t a i n l e s s s t e e l - - t h e c o r r o s i o n p r o t e c t i o n p r o v i d e d by the o x i d e t o s u p e r h e a t e d steam is v e r y markedly increased.
T h i s element a l s o i n c r e a s e s r e s i s t a n c e
t o o x i d a t i o n by g a s e s - - a i r , oxygen, and c a r b o n d i o x i d e .
Aluminum is an e f f e c t i v e a l l o y i n g c o n s t i t u e n t f o r imp r o v i n g the c o r r o s i o n - o x i d a t i o n r e s i s t a n c e o f i r o n as
w e l l . 'The p r o t e c t i v e f i l m is e n r i c h e d in aluminum
as compared t o the m e t a l c o m p o s i t i o n .
In both systems,
the a l l o y s c o n t a i n i n g aluminum t e n d t o be b r i t t l e .
I have been t a l k i n g t o you about the f o r m a t i o n o f
o x i d e f i l m s ; f o r c o m p l e t e n e s s i t is a p p r o p r i a t e t o
m e n t i o n t h a t f i l m s a l s o grow o r f o r m by r e c r y s t a l l i z a t i o n o f a s u b s t r a t e l a y e r o r by h y d r a t i o n o f a materi a l t h a t was o r i g i n a l l y formed in an anhydrous form.
As a g e n e r a l r u l e , t h o s e c a s e s produce f i l m s t h a t a r e
not h i g h l y p r o t e c t i v e . There is a p r a c t i c a l e x c e p t i o n
t o t h a t : i f one a n o d i z e s aluminum in some e n v i r o n m e n t s ,
n o t a b l y s u l f u r i c a c i d , the c o a t i n g is r e l a t i v e l y p o r o u s ,
w i t h the o x i d e o n l y p a r t i a l l y h y d r a t e d . By b o i l i n g in
w a t e r , h y d r a t i o n is i n c r e a s e d , the volume o f the o x i d e
is i n c r e a s e d and the p o r e s a r e s e a l e d , and an e f f e c t i v e
p r o t e c t i v e l a y e r is formed.
I'd l i k e t o s w i t c h now and t a l k t o you about degr a d a t i o n of f i l m s .
I n o r d e r t o t a l k about c o r r o s i o n
one has t o c o n s i d e r b o t h the growth o f f i l m s and t h e i r
degradation.
As one s t u d i e s them, one f i n d s t h a t the
c o m b i n a t i o n o f the two is the key t o g e t t i n g a measure
o f u n d e r s t a n d i n g o f the b e h a v i o r o f the system. Some
o f the r e s u l t s a r e a l i t t l e u n e x p e c t e d at f i r s t g l a n c e .
2

7.
DRALEY
Corrosion
of Valve
197
Metals
%AI
Metal Loss, mg/cm
18.0
17.0
8.8
0.06
Samples exposed in as cast condition, surfaces electropolished.

Corrosion
Figure 10.
Corrosion of aluminum-modified Type 304 S S for 28 days in steam

contg. 30 ppm 0 at 650C (8)
2
20
40
60
80
IOO
120
140
160
TIME, days
Figure 11.
Parabolic corrosion of experimental aluminum alloy A288 (Al + 1%

Ni, 0.5% Fe, 0.1% Ti)instagnant waterat260C (9)

CORROSION
198
CHEMISTRY
I t is w e l l f o r us t o be a l e r t f o r such t h i n g s . L e t me
make an o b v i o u s p l a t i t u d e f o r y o u about a f i l m t h a t
degrades at a c o n s t a n t r a t e .
I t is o b v i o u s t h a t t h e
m e t a l w i l l c o r r o d e at a c o n s t a n t r a t e i f d e g r a d a t i o n
is u n i f o r m a l l o v e r t h e s u r f a c e , a l t h o u g h i t m i g h t
t a k e some time t o r e a c h t h a t s t a g e w h i l e i t b u i l d s up
a film.
That is n o t a r a r e phenomenon. I t is more
common, I t h i n k f o r d e g r a d a t i o n n o t t o be t h a t u n i f o r m
o v e r t h e s u r f a c e . We're g o i n g t o t a l k about some o f
those cases.
F i r s t , l e t us c o n s i d e r a r a t h e r s i m p l e c a s e : t h e
f i l m d i s s o l v e s in w a t e r .
When i r o n o r s t e e l c o r r o d e s
in h i g h t e m p e r a t u r e w a t e r w i t h o u t oxygen, t h e r a t e o f
c o r r o s i o n is d e t e r m i n e d by t h e r a t e at w h i c h t h e f i l m
d i s s o l v e s and is l o s t from t h e s u r f a c e . T h i s r a t e
remains c o n s t a n t i f t h e r e is some p r o c e d u r e t h a t c l e a n s
up t h e w a t e r and keep
such p r o c e d u r e is passag t h r o u g
p
g
l o w e r t e m p e r a t u r e septum in w h i c h some o f t h e m a t e r i a l
p r e c i p i t a t e s . A n o t h e r is passage t h r o u g h an i o n exchange r e s i n o r some o t h e r d e v i c e t h a t w i l l p u r i f y
the w a t e r .
Such l o o p systems o f t e n c o n t a i n suspended
s o l i d c o r r o s i o n p r o d u c t in t h e w a t e r .
This m a t e r i a l
in n u c l e a r r e a c t o r systems is c a l l e d c r u d and i t has
been t h e s o u r c e o f a l o t o f i r r i t a t i o n and money.
These come about because t h e c r u d is r a d i o a c t i v e and
d e p o s i t s in a l l p a r t s o f t h e system, c o m p l i c a t i n g
maintenance.
I f one chooses t h e t e m p e r a t u r e and t h e a l l o y ( e . g .
A288 c o n t a i n i n g 1% N i ) aluminum forms in w a t e r a f i l m
such t h a t t h e r a t e o f f o r m a t i o n is i n v e r s e l y p r o p o r t i o n a l t o t h e t h i c k n e s s . That g i v e s what's c a l l e d t h e
p a r a b o l i c g r o w t h l a w ; d a t a f o r such b e h a v i o r a r e shown
in F i g u r e 11 ( t o g e t h e r w i t h a dashed c u r v e f o r a n o t h e r
experiment).
I n t h e k i n d o f system in riich f r e s h w a t e r
is c o n t i n u o u s l y added and t h e e x c e s s a l l o w e d s i m p l y t o
l e a k o u t , at l e a s t a p a r t i a l l y s a t u r a t e d s o l u t i o n is
l o s t a l l o f t h e t i m e . The two specimens o f F i g u r e 12
have been f i t t e d by c u r v e s t h a t have t h e same growth
r a t e c o n s t a n t as in F i g u r e 11 and d i f f e r e n t d i s s o l u tion rates.
They were in t h e same a u t o c l a v e at s l i g h t l y d i f f e r e n t l o c a t i o n s ; probably the water contained a
l i t t l e more d i s s o l v e d aluminum at one specimen t h a n at
t h e o t h e r . The e x p r e s s i o n f o r t h e p a r a l i n e a r b e h a v i o r
in i t s s i m p l e form is:
dt - L-(g+ft)
'

DRALEY
Corrosion
of Valve
20
Metals
TIME, days
Figure 12.
Paralinear corrosion of aluminum alloy A288 in refreshed water at

260C(9)
1
CORROSION OF ALLOY 255 IN
350 WATER
CONTROL SAMPLES
- 0 . 2 MILS OXIDE REMOVED
- 0.4 MILS OXIDE REMOVED
ol0
20
*-
8
I
40
TIME,
60
80
days
Journal of Nuclear Materials
Figure 13.
Influence of corrosion-oxide removal on the corrosion of an

O.lTi alloy (10)

Al-lNi-
CORROSION
200
CHEMISTRY
where L is t h e amount o f m e t a l l o s s ( d e t e r m i n e d t h r o u g h
t h e use o f a s p e c i a l m e t a l t h i c k n e s s gauge), kp t h e
p a r a b o l i c growth c o n s t a n t , f t h e r a t e o f d i s s o l u t i o n
f o r t h e specimen, and g t h e amount o f d i s s o l u t i o n t h a t
o c c u r s e a r l y in t h e e x p o s u r e . A t l o n g t i m e s t h e c u r v e
f o r L v e r s u s time r e s e m b l e s a s t r a i g h t l i n e w i t h
slope f.
P a r a l i n e a r c o r r o s i o n ( r e l a t e d to d i s s o l u t i o n of
c o r r o s i o n p r o d u c t ) does n o t o c c u r f o r a l l aluminum
a l l o y s in w a t e r at a l l h i g h t e m p e r a t u r e s .
I n F i g u r e 13
are p l o t t e d d a t a f o r an a l l o y ( A l , 1% N i , 0.1% T i )
c o r r o d e d in w a t e r at 350C ( 1 0 ) . The c o r r o s i o n r a t e
was low and c o n s t a n t , as shown b e t t e r in o t h e r f i g u r e s
in the same p u b l i c a t i o n .
F o r some specimens in t h e
f i g u r e 1/3 o r 2/3 o f t h e c o r r o s i o n p r o d u c t was removed
m e c h a n i c a l l y a f t e r t h e f i r s t exposure p e r i o d .
There
was no d i s c e r n i b l e e f f e c
dicating that contro
c l o s e to the m e t a l - o x i d e i n t e r f a c e .
Similar experi
ments f o r t h e a l l o y s and t e m p e r a t u r e s where p a r a l i n e a r
b e h a v i o r o c c u r s showed t h a t removing some o f t h e p r o d u c t caused an i n c r e a s e in subsequent c o r r o s i o n r a t e .
The use o f F i g u r e 14 b e g i n s d i s c u s s i o n about
low t e m p e r a t u r e c o r r o s i o n o f aluminum in w a t e r .
Again
we 11 see t h a t the t o t a l f i l m is n o t c o n t r o l l i n g .
This
is t h e k i n d o f c u r v e o b t a i n e d in a c o u p l e o f t e s t s t h a t
ran f o r a l o n g t i m e in c o n t i n u o u s l y r e f r e s h e d systems.
Note t h a t t h e r a t e is d e c r e a s i n g c o n t i n u a l l y w i t h time
f o r at l e a s t a few y e a r s w e ' l l a n a l y z e t h a t c u r v e
shape s t a r t i n g w i t h F i g u r e 15. A t t h e b e g i n n i n g o f the
t e s t s ( f r o m 0.1 t o n e a r l y 10 h o u r s ) and subsequent t o
about 100 h o u r s , t h e w e i g h t g a i n and t h e m e t a l c o r r o d e d
( d e t e r m i n e d t h r o u g h t h e use o f a s e n s i t i v e m e t a l t h i c k ness gauge) v a r i e d as t h e l o g a r i t h m o f t i m e . The i n i t i a l f i l m is boehmite, t h e same p a r t l y h y d r a t e d o x i d e
t h a t forms at h i g h t e m p e r a t u r e s . When t h i s f i l m b r e a k s
down, b e g i n n i n g in h a l f a day at t h e s e c o n d i t i o n s , we
f i n d t h a t t h e t o t a l amount o f c o r r o s i o n and the t o t a l
o x i d e p r e s e n t q u i c k l y i n c r e a s e s e v e r a l f o l d . The new
p r o d u c t is t h e c o m p l e t e l y h y d r a t e d o x i d e b a y e r i t e . I f
one runs t h e t e s t a l o n g time ( F i g u r e 16) one f i n d s
t h a t t h e l o g a r i t h m i c r a t e law h o l d s . The dashed l i n e s
i n d i c a t e t h a t the i n i t i a l p e r i o d is s e n s i t i v e t o t h e
t e s t p r o c e d u r e t h a t is used.
The h e i g h t o f t h e p l a t e a u v a r i e s i n v e r s e l y w i t h how w e l l r e f r e s h e d t h e s o l u tion
is.
The r e q u i r e m e n t f o r measurement s e n s i t i v i t y
in t h i s t e s t was s u b s t a n t i a l . As a m a t t e r o f f a c t ,
t h e (eddy c u r r e n t ) gauge l i m i t a t i o n came n o t by i t s
s e n s i t i v i t y (about t e n Angstrom u n i t s in d i a m e t e r f o r
1

DRALEY
Corrosion
of Valve
200
Metals
201
40
TIME , days
U.S. Atomic Energy Commission and
European Atomic Energy Society
Figure 14.
Corrosion experiments in water at two oxygen concentrations (< 0.4

and 19mg/L) (11)
0.1
10
100
TIME, hours
U.S. Atomic Energy Commission and

European Atomic Energy Society
Figure 15.
Early stagesincorrosion of aluminum (11)

1000
CORROSION

CHEMISTRY
7.
DRALEY
Corrosion
of
Valve
Metals
203
a r o u n d specimen) b u t because o f the m e t a l l u r g i c a l

changes t h a t o c c u r r e d in the samples.
Now I'd l i k e t o a n a l y z e what happens t o the o x i d e
d u r i n g the second l o g a r i t h m i c c o r r o s i o n p e r i o d .
Fig
u r e 17 shows the amount o f aluminum d i s s o l v e d f r o m a
specimen (1100 aluminum) and c a r r i e d away in the d i s
charge w a t e r . T h i s was d e t e r m i n e d by v e r y c a r e f u l l y
c o l l e c t i n g the e f f l u e n t s o l u t i o n , b o i l i n g o f f the
w a t e r , c o l l e c t i n g the aluminum, and a n a l y z i n g the
m i c r o g r a m q u a n t i t i e s . D i s s o l u t i o n (amount = ) oc
c u r r e d at a c o n s t a n t r a t e d u r i n g the second l o g a r i t h
mic p e r i o d . Combining t h e s e d a t a w i t h w e i g h t g a i n (G)
and m e t a l l o s t f r o m t h e s i n g l e specimen (L) , the amount
o f boehmite (a) and t h e amount o f b a y e r i t e (b) shown
in F i g u r e 18 were c a l c u l a t e d ( 1 3 ) . The c u r v e f o r
boehmite l a y e r growth c l o s e t o the m e t a l c l o s e l y f o l
lows the c u r v e f o r th
showing an a t y p i c a
w h i l e the amount o f b a y e r i t e s l o w l y d e c r e a s e s (presum
a b l y by d i s s o l u t i o n ) .
The e v i d e n c e is t h a t in t h i s
system boehmite makes a p r o t e c t i v e ( r a t e - c o n t r o l l i n g )
l a y e r w h i l e the b a y e r i t e d i s s o l v e s and o b s c u r e s the
truth.
I w o u l d l i k e t o t e l l you about a n o t h e r k i n d o f
u n u s u a l k i n e t i c b e h a v i o r , t h a t o f z i r c o n i u m . An a l l o y
c a l l e d Z i r c a l o y 2 c o n t a i n s m i n o r amounts o f i r o n ,
chromium and n i c k e l and a l i t t l e t i n . The a l l o y was
i n v e n t e d by a c c i d e n t a l l y c o n t a m i n a t i n g a z i r c o n i u m tin alloy with stainless steel.
Since t h a t time
p e o p l e have been making i t on p u r p o s e . The w e i g h t g a i n s l o p e s on t h e l o g - l o g p l o t in F i g u r e 19 a r e
a p p r o x i m a t e l y 1/3 and t h e r a t e e x p r e s s i o n t h a t is
n e a r l y f o l l o w e d is c a l l e d c u b i c o x i d a t i o n . I t o c c u r s
i n i t i a l l y in w a t e r ; i t is f o l l o w e d by f i l m breakdown
and an i n c r e a s e in o x i d a t i o n r a t e w i t h new k i n e t i c s
(showing s t r a i g h t l i n e s and s l o p e s v e r y c l o s e t o 1
on t h i s p l o t ) . A l o g - l o g s t r a i g h t l i n e w i t h a s l o p e
o f one is u n u s u a l , s i n c e i t r e q u i r e s the p a r t i c u l a r
s t r a i g h t l i n e on c a r t e s i a n c o o r d i n a t e s t h a t p a s s e s
t h r o u g h t h e o r i g i n . A t the t i m e o f "breakaway" t h e r e
is a r e c r y s t a l l i z a t i o n o f the z i r c o n i u m o x i d e t o a
l e s s coherent f i l m .
That is an a d d i t i o n a l f o r m o f
degradation.
L e s t you b e l i e v e t h i n g s a r e too s i m p l e d u r i n g
" c u b i c o x i d a t i o n I've chosen t o show t h i s s l i d e
( F i g u r e 20) b a s e d on d a t a by Bob Shannon at H a n f o r d ,
Washington, w h i c h shows t h a t i n d i v i d u a l specimens
c o r r o d e in s e r i e s o f waves. P a u l P e m s l e r once c h r i s
tened those the P i c t u r e s q u e H i l l s o f Shannon d u r i n g a
m e e t i n g . What t h i s i l l u s t r a t e s is t h a t we're n o t
1 1

204

Figure 17.
Corrosion product dissolved from specimen of Figure 18(13)

7.
DRALEY
Corrosion
of Valve
Metals

205
206
10,000 F
Il
- I -'
5
10
'
- - 1 '
.
SO 100
500 1000
Exponrt URN, Dtys
. . I 11
5000 10,000
. . Ii
Westinghouse Atomic Power Division

Figure 19.
Corrosion of beta-quenched Zircaloy-2 in water and steam (14)

DRALEY
Figure 21.
Corrosion
of Valve
Metals
207
Corrosion of an aluminum alloy (1100 Al + 1% Ni) in high-temperature water (9)

CORROSION
208
CHEMISTRY
d e a l i n g w i t h continuous f i l m s c o n t i n u o u s l y growing
w i t h o u t breakdown. I t happens t h a t t h e breakdown
on t h e s e specimens o c c u r r e d o v e r much o f t h e s u r f a c e
at the same t i m e so t h e phenomenon is v i s i b l e .
If i t
o c c u r r e d l o c a l l y and n o t at t h e same t i m e at d i f f e r e n t
p l a c e s , y o u w o u l d n o t see t h e " h i l l s " , b u t odd k i n e t i c s
such as r o u g h l y c u b i c .
The phenomenon is by no means
unique t o zirconium.
F i g u r e 21 shows s i m i l a r b e h a v i o r
by aluminum, a l s o in h i g h t e m p e r a t u r e w a t e r .
The o x i d a t i o n o f z i r c o n i u m in oxygen at e l e v a t e d
temperatures f o l l o w s near-cubic k i n e t i c s f o r awhile,
t h e n p a r a b o l i c k i n e t i c s . A number o f e f f o r t s have been
made t o e x p l a i n t h e n e a r - c u b i c b e h a v i o r , w i t h l o c a l i z e d
o r l i n e d i f f u s i o n as t h a t perhaps g e n e r a l l y p r e f e r r e d .
I ' l l describe f o r yo
and p r e s e n t e d i n f o r m a l l
l i s h e d . A t 700C t h e r e is an i n i t i a l l a y e r o f z i r c o nium o x i d e t h a t is r e l a t i v e l y p e r f e c t , t h a t forms
i n t e r f e r e n c e c o l o r s on s m a l l a r e a s ; t h e r a t e o f growth
o f f i l m and t h e r a t e o f d i f f u s i o n o f oxygen i n t o t h e
m e t a l depend on t h e o r i e n t a t i o n o f t h e m e t a l c r y s t a l .
P o l y c r y s t a l l i n e specimens p r e p a r e d m e t a l l u r g i c a l l y
in d i f f e r e n t ways, always p u r e and e q u a l l y c a r e f u l l y
t r e a t e d , o x i d i z e at q u i t e d i f f e r e n t r a t e s i n i t i a l l y ,
but t h e r a t e s become e q u a l at l o n g ( p a r a b o l i c ) t i m e s .
To f i t t h e s e f a c t s I d e v e l o p e d t h e f o l l o w i n g model.
The f i l m t h a t grows on t h e m e t a l s u r f a c e is p r o p o s e d
t o be u n i q u e and d i f f e r e n t from t h e one t h a t is s t a b l e
on t h e o u t s i d e and at l o n g t i m e s .
X-ray d i f f r a c t i o n
p a t t e r n s t a k e n in o u r l a b o r a t o r y d u r i n g i n i t i a l o x i d a t i o n ( s p e c i a l apparatus) suggest t h a t t h i s oxide
is t e t r a g o n a l r a t h e r t h a n t h e commonly found monoc l i n i c oxide.
A t any s m a l l a r e a on t h e s u r f a c e , f o r
example f o r a s i n g l e c r y s t a l s u r f a c e , t h e i n i t i a l f i l m
grows and oxygen d i f f u s e s i n t o t h e m e t a l at r a t e s t h a t
are unique f o r that area u n t i l the f i l m t h i c k n e s s
r e a c h e s t h e v a l u e s ( p r o p o s e d t o be t h e same f o r a l l
areas).
The i n i t i a l f i l m t h e n t r a n s f o r m s n e a r l y ins t a n t a n e o u s l y i n t o f i n a l f i l m , and t h e i n i t i a l f i l m
t h e n grows a g a i n in a second c y c l e , a g a i n t o t h e
l i m i t i n g t h i c k n e s s s. The p a r a b o l i c r a t e c o n s t a n t
f o r t h e f i n a l f i l m is c ( v a l u e t h e same f o r a l l a r e a s )
and t h e r a t e o f growth o f i n i t i a l f i l m at a p a r t i c u l a r
a r e a is
t

7.
DRALEY
Corrosion
of Valve
Metals
209
where is t h e number o f t h e growth c y c l e at t i m e t and

kj_ is t h e l o c a l d i f f u s i o n c o n s t a n t f o r oxygen in m e t a l .
An e s t i m a t e o f t h e t y p e o f o x i d a t i o n c u r v e t o be
e x p e c t e d f r o m t h i s model was d e v e l o p e d f r o m an i n i t i a l
case where two t y p e s o f s u r f a c e s (A and B) were i d e n
t i f i e d , and r a t e c o n s t a n t s a s s i g n e d t h a t were n o t in
c o n f l i c t w i t h any known d a t a .
Weight g a i n s e x p e c t e d
f o r t h e f i r s t thousand m i n u t e s a r e shown in F i g u r e 22
f o r a r e a s A and and f o r a specimen c o n s i s t i n g o f 80%
t y p e A and 20% t y p e B. The ends o f t h e f i r s t growth
c y c l e f o r each a r e a c a n be i d e n t i f i e d . A number o f
w e i g h t - g a i n p o i n t s f o r t h i s h y p o t h e t i c a l specimen a r e
p l o t t e d in F i g u r e 23 a l o n g w i t h a r e p r o d u c e d w e i g h t
gain recorder t r a c i n g (the s o l i d l i n e ) .
A perfect
c u b i c l i n e is a l s o shown f o r c o m p a r i s o n (dashed l i n e ) .
The f i t is so good t h a t i t
highl
likel
t h a t t h e use o f mor
average in t h e mode
g
of real-sample data.
I t i s n ' t p o s s i b l e t o s a y much
more at t h i s t i m e ; I do b e l i e v e t h a t t h e w e i g h t - g a i n
c u r v e f o r t h e s i n g l e c r y s t a l w a f e r (more t h a n 8 0 % o f
a r e a o f one o r i e n t a t i o n ) shown in F i g u r e 24 d i s p l a y s
b r e a k s and s l o p e s o f t h e r i g h t o r d e r f o r t h e segments
on a l o g - l o g p l o t . My p e r s o n a l c o n v i c t i o n is t h a t some
k i n d o f s t a t i s t i c a l models a r e g o i n g t o be r e q u i r e d t o
f i t c o r r e c t l y much o f t h e c o r r o s i o n and o x i d a t i o n d a t a
of the valve metals.
You've h e a r d e l e c t r o c h e m i s t r y o f c o r r o s i o n as a
l e c t u r e ; I s h o u l d n ' t spend much t i m e on i t b u t I ' d
l i k e t o d e s c r i b e some e l e c t r o c h e m i c a l e f f e c t s f o r f i l m
formers. F i r s t the general p r i n c i p l e s . I f you put a
good e l e c t r o n i c c o n d u c t o r ( a m e t a l ) in an aqueous s o l u
t i o n , y o u w i l l t y p i c a l l y f i n d t h a t an e l e c t r i c a l p o t e n
t i a l is d e v e l o p e d between t h e p i e c e o f c o n d u c t o r and
the s o l u t i o n . When i o n s o f t h e m e t a l e n t e r t h e s o l u t i o n
and l e a v e e x t r a e l e c t r o n s b e h i n d a n e g a t i v e p o t e n t i a l is
d e v e l o p e d . A l l o x i d a t i o n r e a c t i o n s o c c u r r i n g on t h e
s u r f a c e a r e e x p e c t e d t o produce t h i s r e s u l t .
Similarly,
r e d u c t i o n r e a c t i o n s t h a t use e l e c t r o n s f r o m t h e m e t a l
a r e e x p e c t e d t o p r o d u c e a more p o s i t i v e p o t e n t i a l in
the m e t a l . The s o l u t i o n p o t e n t i a l o f t h e m e t a l i n f l u
ences t h e r a t e o f an e l e c t r o c h e m i c a l h a l f - c e l l r e a c t i o n
in a c c o r d a n c e w i t h L e C h a t e l i e r ' s P r i n c i p l e , so i t is
p o s s i b l e t o p r e d i c t t h r o u g h t h e use o f t h e N e r n s t Equa
t i o n t h e p o t e n t i a l t h a t w i l l e x i s t when t h e o n l y s i g n i
f i c a n t l y r a p i d r e a c t i o n s a r e t h e o x i d a t i o n and r e d u c t i o n
p a r t s o f a r e v e r s i b l e r e a c t i o n . When more t h a n one
p o t e n t i a l l y r e v e r s i b l e process occurs, the r a t e of o x i
d a t i o n w i l l be e x p e c t e d t o exceed t h e r a t e o f r e d u c t i o n
f o r at l e a s t one and t h e c o n v e r s e f o r at l e a s t one. A t

210

DRALEY
Corrosion
of Valve
Metals

212
CORROSION
CHEMISTRY
a s t e a d y - s t a t e p o t e n t i a l , the sum o f the r a t e s o f a l l

o f the a n o d i c r e a c t i o n s w i l l e q u a l the sum o f the r a t e s
o f a l l the c a t h o d i c r e a c t i o n s .
F o r f i l m f o r m e r s , a t y p i c a l a n o d i c r e a c t i o n is
M + H0
> MOH
+ H
+ e" ,
so an o x i d e is formed and t h e s o l u t i o n becomes a c i d .

The most common c a t h o d i c r e a c t i o n s a r e
H0
+ e"
1/2
1/2
+ OH"
+ 2H 0 + 2e~ + 20H"
2
and
,
so c a t h o d i c r e a c t i o n s produce a l k a l i .
Directly related
t o the pH a r e the s t a b i l i t i e s o f the v a r i o u s s p e c i e s
f o r the c o r r o d i n g m e t a l
P o u r b a i x Diagram f o
pH zones in w h i c h F e 0 o r F e ( 0 H ) a r e s t a b l e and thus
in w h i c h p r o t e c t i v e f i l m s o f t h e s e s u b s t a n c e s m i g h t
f o r m at a t o t a l i o n i c c o n c e n t r a t i o n o f 10"
M.
When a f i l m is p r e s e n t , the hydrogen p r o d u c e d from
the second r e a c t i o n above is n o t n e c e s s a r i l y a l l l i b e r ated d i r e c t l y i n t o the water or s o l u t i o n .
Some o f i t
may be l i b e r a t e d b e n e a t h the f i l m as shown in F i g u r e 26.
The r e s u l t may be l o c a l r u p t u r i n g o f the o x i d e f i l m - a form of degradation--the f o r m a t i o n of metal h y d r i d e ,
o r the e n t r y o f hydrogen i n t o t h e m e t a l , depending on
w h i c h a r e f e a s i b l e o r most f a v o r a b l e . I b e l i e v e t h e r e
a r e a number o f cases where f i l m r u p t u r e o c c u r s , a l though they a r e o f t e n n o t easy t o i d e n t i f y . We have
d e c l a r e d the b e l i e f t h a t i t is i m p o r t a n t in the c o r r o s i o n o f aluminum a l l o y s below the b o i l i n g p o i n t o f
w a t e r ( 1 9 ) . To p r o v i d e e v i d e n c e o f t h i s , we r a n a ser i e s o f e x p e r i m e n t s t o d e t e r m i n e the l o g a r i t h m i c c o r r o s i o n r a t e c o n s t a n t f o r 1100 aluminum at 70C w i t h pot e n t i a l s c o n t r o l l e d by a s p e c i a l i n t e r r u p t i n g p o t e n t i o s t a t ( 2 0 ) . The r e s u l t s , in F i g u r e 27, show t h a t
a n o d i c p o l a r i z a t i o n (diamond-shaped p o i n t s ) caused
lower c o r r o s i o n r a t e s t h a n the u n p o l a r i z e d runs ( c i r c u l a r p o i n t s ) . A r e d u c t i o n in c a t h o d i c damage t o the
f i l m is s u g g e s t e d . The p o t e n t i a l above w h i c h hydrogen
s h o u l d n o t be l i b e r a t e d cannot be i d e n t i f i e d because
the l o c a l pH d u r i n g a n o d i c p o l a r i z a t i o n c o u l d be cons i d e r a b l y below the 6+ o f the d i s t i l l e d w a t e r at 70.
We s h a l l see something e n l i g h t e n i n g on t h i s l a t e r .
For
pH 6 the p o t e n t i a l f o r the r e v e r s i b l e hydrogen l i b e r a t i o n r e a c t i o n is c a l c u l a t e d t o be about -0.4 v o l t .
Most n o t a b l y at h i g h e r t e m p e r a t u r e s , aluminum a l s o
s u f f e r s f r o m the e n t r y o f c o r r o s i o n p r o d u c t i n t o the
2

7.
DRALEY
Corrosion
of Valve
213
Metals
Marcel Dekker, Inc.

Figure 25.
Pourbaix diagram for the system Fe-H 0 at 25 C (17)

2

214
CORROSION
CHEMISTRY

Figure 26.
-0.5
Schematic of corrosion processes (IS)
-0.4
-0.3
-0.2
SOLUTION POTENTIAL,
Figure 27.
V.
-0.1
Vs.
STD.
0
HYD.
+0.1
ELEC.
Effect of controlled-solution potential on logarithmic corrosion-rate

constant for aluminum (12)

7.
DRALEY
Corrosion
of
Valve
215
Metals
metal.
I n F i g u r e 28 a r e shown specimens o f commerc i a l l y p u r e aluminum a f t e r two weeks exposure t o w a t e r
at 275C. The b l i s t e r i n g p r o g r e s s e s w i t h more s e v e r e
exposure c o n d i t i o n s , as shown in F i g u r e 29 (66 h o u r s ,
300C). Some o f the b l i s t e r s a r e h o l l o w b e f o r e the
w a t e r g a i n s a c c e s s and b e f o r e they become o x i d e - m e t a l
m i x t u r e s . F i g u r e 30 shows what happens at a h i g h e r
t e m p e r a t u r e ; t h i s exposure was f o u r hours at 315C.
I f v a r y i n g amounts o f m a t e r i a l a r e e t c h e d from t h e
s u r f a c e o f a s e r i e s o f samples c o r r o d e d f o r a b r i e f
p e r i o d , and each r e m a i n i n g sample is a n a l y z e d f o r hydrogen c o n t e n t , the hydrogen in t h e e t c h e d - o f f l a y e r s
can be c a l c u l a t e d .
The r e s u l t s in F i g u r e 31 show t h a t
the hydrogen c o n t e n t o f the s u r f a c e l a y e r s i n c r e a s e d
q u i t e a b i t , and demonstrate t h a t the gas t h a t formed
t h e b l i s t e r s was hydrogen
I f t h e h y d r o g e n is produced
l a r g e l y at a p o s i t i o
as in F i g u r e 32, th
t h i s c a s e , the aluminum is s i m p l y b o l t e d t o a p i e c e
of s t a i n l e s s s t e e l .
Exposure c o n d i t i o n s were as in
F i g u r e 30.
I f t o the w a t e r a r e added i o n s t h a t a r e
r e d u c i b l e t o m e t a l ( l a r g e l y at a c t i v e cathode s p o t s )
m e t a l d e n d r i t e s a r e formed. The n i c k e l d e n d r i t e s in
F i g u r e 33 were formed in t h i s way; no s e v e r e c o r r o s i o n
o f 1100 aluminum was o b s e r v e d d u r i n g c o r r o s i o n exposure
t o s t a b l e n i c k e l s a l t s o l u t i o n s at e l e v a t e d temperat u r e s . F i g u r e 34 s u g g e s t s t h a t i f d e p o s i t s o f somet h i n g l i k e t h e n i c k e l - a l u m i n u m compound N i A l were
u s e d t h e y w o u l d a c t as v e r y e f f e c t i v e cathodes f o r
hydrogen l i b e r a t i o n .
F o r t h i s r e a s o n , we made aluminumn i c k e l a l l o y s in w h i c h N i A l p r e c i p a t e d . As i n d i c a t e d
in F i g u r e 35, some 1% n i c k e l a l l o y s showed e x c e l l e n t
c o r r o s i o n r e s i s t a n c e in h i g h t e m p e r a t u r e w a t e r .
I won't
d i s c u s s d e t a i l s o f c o m p o s i t i o n and m e t a l l u r g i c a l p r e p a r a t i o n ; t h e y were f o u n d t o be i m p o r t a n t .
Uranium c o r r o d e s in o x y g e n - f r e e w a t e r at a c o n s t a n t
r a t e t o f o r m U0 in t h e form o f a r e l a t i v e l y u n p r o t e c t i v e l a y e r ; F i g u r e 36 shows such c o r r o s i o n r a t e s on an
A r r h e n i u s p l o t . When the r a t e g e t s v e r y l a r g e at e l e v a t e d t e m p e r a t u r e s , u r a n i u m h y d r i d e can be found m i x e d
in w i t h t h e o x i d e powder. I f oxygen is p r e s e n t in the
water, f o r a long p e r i o d p r o t e c t i v e oxide f i l m s are
formed; t h e s e e v e n t u a l l y break down l o c a l l y and s p r e a d .
F i g u r e 37 shows t h a t t h e whole s u r f a c e e v e n t u a l l y becomes bad.
We b e l i e v e t h a t some h y d r i d e was r e g u l a r l y
formed b e n e a t h t h e o x i d e b o t h in d e a e r a t e d and a e r a t e d
w a t e r , and t h a t the h y d r i d e s u b s e q u e n t l y was c o n v e r t e d
t o t h e more s t a b l e o x i d e . T h i s is b e l i e v e d t o be a
case o f f i l m d e g r a d a t i o n by t h e f o r m a t i o n o f h y d r i d e
beneath i t .
For s e l e c t e d uranium a l l o y s , oxide f i l m s
3

216

Figure 28.
Typical appearance of 1100 aluminum after about two weeksindis

tilled waterat275C (IS)
Corrosion
Figure 29.
Surface of "normal" 1100 aluminum sample after 66 hours in distilled

waterat300C., 20 (21)

DRALEY
Corrosion
of Valve
217
Metals
Corrosion
Figure 30.
1100 aluminum after four hoursindistilled waterat315C (22)
TREATMENT
AVERAGE
METAL
ETCHED
AWAY
HYDROGEN
CONTENT
(WHOLE
SAMPLE)
12.1 ppm
AS CORRODED
ESTIMATE OF
HYDROGEN IN
INCREMENTS OF
ETCHED METAL
7.3
ETCHED (DILUTE HNO3-HF)
0.016 mm
3.0
ETCHED
0.041
1.8
59
ETCHED
0.071
1.1
24
ETCHED
0.120
1.0
ETCHED
0.22
0.8
0.6
AS STRIPPED
BLANK (NO CORROSION)
280 ppm
Argonne National Laboratory

Figure 31.
Hydrogen analyses of 1100 aluminum after two days corrosion in

waterat290C (23)

218
Corrosion
Figure 32.
1100 aluminum,
distilled waterat315C (22)
Figure 33.
Dendritic nickel deposited on 1100 aluminum from N i S 0

(50ppmNi )250X
(21)
Corrosion
4
solution
++

Corrosion
DRALEY
219
of Valve Metals
FeAI
C
J -.5
--^^
FeNiAI,
-.4
1 *
Ni AU
^ -
>
-.2
'
.-
A - " ^
A
TEMPERATURE: 2 9 0 C
MEDIUM: DISTILLED WATER
20
CATHODIC
Figure 34.
30
I
10
40
50
60
POLARIZING CURRENT, ^/cm
70
80
Cathodic polarization curves for some aluminum intermetallic com

pounds (9)
'X800l-350C
LINE REPRESENTS
~b DATA OF DILLON
'
U\A/_CIQ/1Q >
AQUEOUS CORROSION OF ALUMINUM ALLOY 288

IAEA Conf. Corrosion of Reactor Materials
Figure 35.
Aqueous corrosion of aluminum alloy A288 (Al -\- 1% Ni, 0.5% Fe,
0.1% Ti) (24)

220

Figure 36.
Corrosion rate of uraniuminhydrogen-saturated water (25)

7. D R A L E Y
Corrosion
of Valve
Metals
221

Figure 37.
Corrosion of uraniuminaerated distilled water (26)

222
a r e p r o t e c t i v e even in the absence o f oxygen, and f o r

v e r y l o n g p e r i o d s . F i g u r e 38 shows some c o r r o s i o n
r a t e s w h i c h a r e r e s p e c t a b l y low.
The maximum tempera t u r e shown is 400C. These f i l m s a l s o b r e a k down
e v e n t u a l l y , and t h i s appears t o i n v o l v e the f o r m a t i o n
o f some u r a n i u m h y d r i d e l o c a l l y .
The breakdown c e r t a i n l y i n v o l v e s the b u i l d u p o f hydrogen in the m e t a l .
F o r the p a r t i c u l a r a l l o y and t e m p e r a t u r e in F i g u r e 39
specimens l a s t e d much l o n g e r b e f o r e damage o c c u r r e d
when they were p r e t r e a t e d in a vacuum b e f o r e c o r r o d i n g .
When z i r c o n i u m is o x i d i z e d in w a t e r , a c o n s i d e r a b l e f r a c t i o n o f the c o r r o s i o n p r o d u c t hydrogen e n t e r s
the m e t a l .
There is e v i d e n c e t h a t the o x i d e r e c r y s t a l l i z a t i o n and the t r a n s i t i o n in k i n e t i c s t h a t were
shown in F i g u r e 19 a r e r e l a t e d t o a b u i l d u p o f h y d r o gen in the s u r f a c e o f the m e t a l
I t has been s u g g e s t e d
t h a t at t h a t time som
the f i l m .
The a d d i t i o
form a c t i v e c a t h o d e s f o r hydrogen l i b e r a t i o n have r e duced hydrogen u p t a k e , have d e l a y e d t r a n s i t i o n , and
have r e s u l t e d in the f o r m a t i o n o f more c o h e r e n t o x i d e
after transition.
There has been no c l e a r r e s o l u t i o n
as t o mechanisms ( 2 9 ) .
I t is p o s s i b l e t o c o n s i d e r gaseous o x i d a t i o n p r o d u c i n g a s t a b l e o x i d e f i l m as an e l e c t r o c h e m i c a l p r o cess in w h i c h o x i d a t i o n o c c u r s at the m e t a l - o x i d e i n t e r f a c e where m e t a l i o n s l e a v e the m e t a l (see F i g u r e 4)
and r e d u c t i o n o c c u r s at the o u t e r s u r f a c e o f the o x i d e
where e l e c t r o n s combine w i t h oxygen. On the b a s i s o f
t h i s l i n e o f r e a s o n i n g i t is p o s s i b l e t o p r e d i c t
(a) the f o r m a t i o n o f a p o t e n t i a l d i f f e r e n c e between
m e t a l and o x i d e e x t e r i o r f o r t h o s e systems in w h i c h
the r e s i s t a n c e o r r e t a r d a n c e
t o the passage o f i o n s
t h r o u g h the g r o w i n g o x i d e is n o t much g r e a t e r t h a n the
r e t a r d a n c e t o the passage o f e l e c t r o n s , and (b) a
change in o x i d a t i o n r a t e f r o m the a p p l i c a t i o n o f an
e l e c t r i c a l p o t e n t i a l between m e t a l and o x i d e e x t e r i o r .
An i l l u s t r a t i o n is the b e h a v i o r o f z i r c o n i u m f o r w h i c h
a p o t e n t i a l in e x c e s s o f one v o l t can be measured
( F i g u r e 40) and whose o x i d a t i o n r a t e at p o i n t s
of
e l e c t r i c a l c o n t a c t can be m a r k e d l y i n f l u e n c e d ( F i g u r e 4 1 ) . The c o n t a c t c o n s i s t e d o f p o i n t s at w h i c h the
specimen r e s t e d upon c o n d u c t i n g powder. S i n c e the
a r e a o f c o n t a c t d i m i n i s h e d under s h a r p e n i n g p o i n t s
o f a n o d i c a l l y s t i m u l a t e d growth and i n c r e a s e d where
g r o w t h was r e t a r d e d c a t h o d i c a l l y , the r a t e o f w e i g h t
g a i n f o r the e n t i r e specimen in the f i g u r e was c o n s i d e r a b l y more r e d u c e d by a p p l i e d c a t h o d i c c u r r e n t t h a n i t
was a c c e l e r a t e d by a p p l i e d a n o d i c c u r r e n t .
fl
,f

DRALEY
Corrosion
of Valve
223
Metals
1000/T ( K)
e
Figure 38.
Corrosion of uranium alloysinwater (27)
TEST TIME, HOURS

Figure 39.
Effect of gas removal on corrosion in water at 290C of U-5% Zr1V Nb alloy (28)
2

CORROSION CHEMISTRY
224
1.6,

Figure 40.
Potential developed during oxidation of zirconium at 700C
(30)

Figure 41.
Variation in oxidation rate with applied potential: zirconium in oxygen at 700C (30)

7.
DRALEY
Corrosion
of
Valve
Metals
225
B e f o r e we f i n i s h , I'd l i k e t o spend a few m i n u t e s

on p i t t i n g .
As you know, t h e r e a r e l o c a l s i t e s at
w h i c h c o r r o s i v e a t t a c k o c c u r s f o r some systems p r e f erentially.
I f t h i s l o c a l attack continues, quite
deep p i t s can form. T h i s is one o f the i n s i d i o u s
k i n d s o f c o r r o s i o n a t t a c k f o r a m a t e r i a l . Some o f
the f i l m - f o r m i n g m e t a l s t e n d t o be q u i t e s u s c e p t i b l e
to p i t t i n g a t t a c k under a p p r o p r i a t e c o n d i t i o n s .
One
o f the c h a r a c t e r i s t i c r e q u i r e m e n t s f o r i t is the format i o n o f low pH w i t h i n a p r o t e c t e d p i t p r o t e c t e d in
some way f r o m the g e n e r a l e n v i r o n m e n t . We t h i n k t h a t
commonly t h e r e a r e l o c a l cathodes at w h i c h hydrogen
l i b e r a t i o n is v e r y g r e a t , at w h i c h f i l m r u p t u r e o c c u r s .
T h i s is made e a s i e r by the f a c t t h a t the cathodes a r e
o f t e n a second, c a t h o d i c phase so t h e r e is o f t e n an
i m p e r f e c t i o n in the o x i d e at the p o i n t anyhow
At
f i r s t t h e r e is a h i g
cathode because o f th
r e a c t i o n has u n d e r c u t the c a t h o d i c p a r t i c l e d e s t r o y i n g
e l e c t r i c a l c o n t a c t , the two h a l f - c e l l r e a c t i o n s w i l l
no l o n g e r be v e r y c l o s e t o g e t h e r and t h e r e w i l l be pH
changes so t h a t the anode a r e a w i l l become a c i d .
The
r e s u l t o f t h i s is t h a t a p r o t e c t i v e f i l m doesn't form
as a p r i m a r y p r o d u c t o f the r e a c t i o n ; i n s t e a d , m e t a l
i o n s a r e formed in s o l u t i o n . As t h e s e i o n s d i f f u s e
out t o the s u r f a c e o f the o x i d e f i l m , the environment
becomes more n e a r l y n e u t r a l and o x i d e s p r e c i p i t a t e .
T h i s l e a d s t o the c h a r a c t e r i s t i c b a r n a c l e d appearance
of a p i t , w i t h p r e c i p i t a t e d oxide over i t . In t h i s
way the s o l u t i o n w i t h i n the p i t is i s o l a t e d f r o m the
b u l k s o l u t i o n , and the a c i d i t y can be g r e a t . I f the
b a r n a c l e becomes a s u f f i c i e n t l y e f f e c t i v e b a r r i e r t o
the f l o w o f the i o n i c c u r r e n t w h i c h must pass t h r o u g h
the s o l u t i o n from remote c a t h o d e s , the p i t s t o p s
g r o w i n g . F i g u r e 42 shows the c l e a n e d s u r f a c e o f a
ground p i e c e o f 1100 aluminum a f t e r about 4 h o u r s in
o x y g e n - s a t u r a t e d d i s t i l l e d w a t e r . There a r e o c c a s i o n a l
s m a l l p i t s ( b l a c k in the p h o t o g r a p h ) .
After nearly
two y e a r s exposure ( F i g u r e 4 3 ) , t h e r e a r e no l a r g e
p i t s ; the appearance is as i f e s s e n t i a l l y a l l o f the
s u r f a c e had in t u r n s e r v e d as the l o c a t i o n f o r m i c r o
p i t formation.
The low c o n d u c t i v i t y o f the w a t e r
m i g h t have c o n t r i b u t e d t o e a r l y s t i f l i n g o f p i t g r o w t h
A t h i g h e r m a g n i f i c a t i o n the p i t s ( F i g u r e 44) a r e n o t
u n l i k e l a r g e r ones seen in o t h e r systems. Presumably
a n o t h e r l e c t u r e r in t h i s s e r i e s w i l l g i v e o r has g i v e n
you some d e t a i l s o f p r a c t i c a l p i t t i n g problems and the
most p r o m i s i n g approaches t o c o n t r o l them.
A number o f i n v e s t i g a t o r s have made e f f o r t s t o
measure the pH in p i t s ; v a l u e s as low as 1.5 have

226
U.S. Atomic Energy Commission

and European Atomic Energy Society
Figure 42. Cleaned 1100 aluminum sur
face after 4 A hours in oxygen-saturated
distilled waterat70C., 25 (11)
l
U.S. Atomic Energy Commission

and European Atomic Energy Society
Figure 43. Cleaned 1100 aluminum sur
face after 704 days corrosion in oxygensaturated distilled water at 70C., 25X
(11)

7.
DRALEY
Corrosion
Figure 44.
Electron micrograph of corroded surface of "commercially pure" aluminum (12)
of Valve
Metals

227
228
been r e p o r t e d .
Even exposed t o the b u l k w a t e r , we
found, t h r o u g h the use o f a s p e c i a l e l e c t r o d e a few
t e n t h s o f a m i l l i m e t e r in t i p d i a m e t e r ( F i g u r e 4 5 ) ,
t h a t the pH n e a r specimens o f 1100 aluminum c o r r o d i n g
in d i s t i l l e d w a t e r r e a c h e d v a l u e s below 3 ( F i g u r e 4 6 ) .
Some y e a r s ago, Howard F r a n c i s , t h e n o f the A r mour R e s e a r c h F o u n d a t i o n , made some t i m e - l a p s e m o t i o n
p i c t u r e s o f a p o t e n t i a l map o f the s o l u t i o n n e x t t o
s t e e l and aluminum a l l o y s p i t t i n g in s a l t w a t e r .
The
p r e s e n c e o f some a c t i v e cathode p o i n t s and g r o w i n g p i t s
was r e a d i l y d i s p l a y e d .
I s u g g e s t e d t h a t he r u n the
f i l m backwards t o see whether the a c t i v e p i t s had been
a c t i v e cathodes j u s t b e f o r e t h e i r i n i t i a t i o n .
He
l a t e r t o l d me he had done so, and t h e y had been w i t h
few o r no e x c e p t i o n s .
A t h i g h t e m p e r a t u r e s f i l m breakdown and p i t t i n g
f o r aluminum a l l o y s t a k e
when t h e r e is a h i g
metal surface.
I f t h e r e a r e a l o t o f specimens in the
system, the c o r r o s i o n r a t e is l o w e r t h a n i f the a r e a
is s m a l l . The r e s u l t s o f some e x p l o r a t o r y e x p e r i m e n t s
a r e shown in F i g u r e 47.
A l a r g e a r e a ( f a c t o r o f 20)
o f aluminum a l l o y i n h i b i t e d c o r r o s i o n w h i l e a l a r g e
area of s t a i n l e s s s t e e l d i d not.
The e f f e c t is c e r t a i n l y r e l a t e d t o c o r r o s i o n p r o d u c t in the system
somehow. I n F i g u r e 48 one can see t h a t the c o r r o s i o n
p r o d u c t l o s t f r o m the specimen was s u b s t a n t i a l l y in
e x c e s s o f t h a t w h i c h d i s s o l v e d in the system.
We
t h o u g h t t h a t , at l o c a l p i t s and b r e a k s the c o r r o s i o n
p r o d u c t , as i t r e a c h e d the o x i d e s u r f a c e and was app r o x i m a t e l y n e u t r a l i z e d , was swept away as p a r t i c l e s o f
oxide.
We t h o u g h t t h a t the a d d i t i o n o f c o l l o i d a l
p a r t i c l e s t o the s o l u t i o n w o u l d t e n d t o " p l u g " openi n g s , r e d u c e the l o s s o f o x i d e , and lower the c o r r o s i o n r a t e . F i g u r e 49 shows t h a t when a h y d r a t e d c o l l o i d was i n j e c t e d in t o the system, a v e r y low c o r r o s i o n r a t e was o b t a i n e d .
I n the same system the
e f f e c t s o f p o l a r i z i n g c u r r e n t on c o r r o s i o n r a t e ( F i g u r e 50) a r e s i m i l a r t o what I showed you at low temp e r a t u r e in F i g u r e 27:
a n o d i c p r o t e c t i o n and c a t h o d i c
stimulation.
The message I'd l i k e t o l e a v e w i t h you t o n i g h t
is t h a t some f i l m s a r e v e r y good and v e r y p r o t e c t i v e ,
some f i l m s have b r e a k s in them, and they a r e moderatel y good, some become bad by some o f the s t r a n g e s t
mechanisms: an u n d e r s t a n d i n g o r c o r r o s i o n phenomena
sometimes r e q u i r e s q u i t e a b i t o f i n g e n u i t y .

7.
DRALEY
Corrosion
of Valve
229
Metals
Corrosion
Figure 45.
Glass, silver/silver iodide pH microelectrode (SI)

230
CORROSION
CHEMISTRY
7
2 mm FROM
UPSTREAM
EDGE
--"
2mm FROM
DO\ VNSTREAM
ED(SE
w
^^CENTER
5
X
CL
40
80
TIME, mins
120
160
200
Corrosion
Figure 46.
Effect of position on pH of50C oxygen-saturated water 0.1 mm from

corroding 1100 aluminum (SI)
Figure 47.
Effect on aqueous corrosion of 8001 aluminum at 260C., 7 m/sec

velocity of added surface of aluminium or stainless steel (S2)

7. D R A L E Y
Corrosion
of Valve
231
Metals
Normal (small) Area,

21-day Exposure
Large Area,
28-day Exposure
Average Metal Loss
13.1 mg/cm
4.60 mg/cm
Estimated AI2O3 H2O Produced

(from metal loss)
29.1 mg/cm
10.2 mg/cm
Actual Average Product Remaining
11.6 mg/cm
7.9 mg/cm
Corrosion Product Lost
17.5 mg/cm
2.3 mg/cm
Corrosion Product PresentatEnd of Test

Compared with Total Produced
40%
78%
Aluminum Area
70 cm
1470 cm
Maximum Dissolved Corrosion Product, from

Solubility Data (2 10" g of Al 0 per liter
at 1.5-liters/hr refreshment)
2.4 mg/cm
0.14 mg/cm
Ratio Dissolved to Actual Loss
0.14
0.06
Corrosion RateinLast 7-day Perio

Figure 48.
Comparison of two dynamic corrosion tests. Water at 260C., 7 m/sec

velocity (32).
20
18
16
METAL CORRODED, m
^ 14
_
DISTILLED
î.JV'' *
(run between colloid

experiments below)
00
j*"^
WATER
HYDRATED ALUMINUM OXIDE COLLOID INJECTED:
UPSTREAM
_ -
DOWNSTREAM Q
-
1
"
1
15
^
1
20
25
TIME, days
30
35
40

Figure 49.
Influence of 35-ppm colloid on the aqueous corrosion of 8001 alumi

numat260C., 7 m/sec velocity (32)

232
CORROSION
CHEMISTRY
18
14
DISTILLED WATER
150
50
100
CATHODE
50
INITIAL APPLIED CURRENT,
100
ANODE
150
/cm

Figure 50.
Effects of applied current on corrosion of 8001 aluminumat260C in

flowing water, 5.6 m/sec (32)

7.
DRALEY
Corrosion
of Valve
Metals
233
L i t e r a t u r e Cited
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
V i j h , . ., J. Electrochem. Soc. (1972) 116, 972.

Tajima, S., Baba, ., and Shimura, F. ., E l e c t r o chimica Acta (1967) 12, 955.
Hauffe, K a r l , " O x i d a t i o n of Metals," p. 419, Plenum
Press, New York, New York, 1965.
Hart, R. ., "Morphology of Corundum Films on Alum
inum," Fifth Int. Cong. f o r Electron Microscopy,
Philadelphia, Pennsylvania, Aug. 29 - Sept. 5, 1962,
Paper No. C-10, Academic Press, New York, New York,
1962.
Hart, R. ., and Maurin, J. ., "Growth of Oxide
Nuclei on Iron," Sixth Int. Cong. f o r Electron
Microscopy, Kyoto, Japan, Aug. 28 - Sept. 4, 1966,
p. 539, Maruze
Ruther, W. E.
19, 127t.
Frankenthal, R. P., and Malm, D. L., J. E l e c t r o
chem. Soc. (1976) 123, 186.
Ruther, W. E., Schleuter, R. R., Lee, R. ., and
Hart, R. ., Corrosion (1966) 22, 147.
Ruther, W. ., and Draley, J. E., unpublished work.
Draley, J. E., Ruther, W. E., and Greenberg, S.,
J. Nucl. Matl. (1962) 6, 157.
Draley, J. E., TID-7587, "Aqueous Corrosion of
1100 Aluminum and of Aluminum-Nickel A l l o y s , "
Int. Conf. on Aqueous Corrosion of Reactor Mat'ls.,
Brussels, Oct. 14-17, 1959, p. 165, U. S. Atomic
Energy Commission and European Atomic Energy So
c i e t y , July 1960.
Draley, J. ., Mori, S., and Loess, R., unpub
lished figure.
Mori, S., and Draley, J. E., J. Electrochem. Soc.
(1967) 114, 352.
WAPD-MRP-107, "Pressurized Water Reactor (PWR)
Project Technical Progress Report October 24, 1963January 23, 1964," Westinghouse Atomic Power Div.
Griggs, B., Maffei, H. P., and Shannon, D. W.,
HW-67818, "Multiple Rate Transitions in the Aque
ous Corrosion of Z i r c a l o y , " Hanford Laboratories,
General E l e c t r i c Company, December 20, 1960.
Draley, J. E., unpublished work.
Diggle, John W. (Ed.), "Oxides and Oxide Films,"
Vol. 1, p. 38, Marcel Dekker, Inc., New York,
New York, 1972.
Draley, J. E., and Ruther, W. E., J. Electrochem.
Soc. (1957) 104, 329.
Draley, J. ., and Mori, Shiro, and Loess, R. E.,
J. Electrochem. Soc. (1963) 110, 622.

CORROSION CHEMISTRY
234
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
Youngdahl, C. ., and Loess, R. E., J. E l e c t r o

chem. Soc. (1967) 114, 489.
Draley, J. E., and Ruther, W. E., Corrosion (1956)
12, 480t.
Draley, J. E., and Ruther, W. E., Corrosion (1956)
12, 441t.
Draley, J. E., and Ruther, W. E., ANL-5658 "Exper
iments in Corrosion Mechanism: Aluminum at High
Temperatures," Argonne National Laboratory,
A p r i l 1957.
Draley, J. E., and Ruther, W. E., "The Corrosion
of Aluminum A l l o y s in High Temperature Water,"
IAEA Conf. Corrosion of Reactor Materials,
Salzburg, June 1962, Vol. I, p. 477.
McWhirter, J. W., and Draley, J. E., ANL-4862
"Aqueous Corrosio
of Project L i t e r a t u r e ,
tory, May 14, 1952.
Mollison, W. ., English, G. C., and Nelson, F.,
CT-3055 "Corrosion of Tuballoy in Distilled Water,"
Argonne National Laboratory, June 23, 1945.
Greenberg, S., and Draley, J. E., unpublished
figures.
Draley, J. E., Greenberg, S., and Ruther, W. .,
J. Electrochem. Soc. (1960) 107, 732.
Parfenov, B. G., Gerasimov, V. V., and Venediktova,
G. I., "Corrosion of Zirconium and Zirconium
A l l o y s , " Translated from Russian by Ch. Nisenbaum,
I s r a e l Program f o r S c i e n t i f i c Translations,
Jerusalem, 1969.
Bradhurst, D. ., Draley, J. E., and Van Drunen,
C. J., J. Electrochem. Soc. (1965) 112, 1171.
Mori, S. Loess, R. E., and Draley, J. E., Corro
sion (1963) 19, 165t.
Draley, J. E., and Ruther, W. E., ANL-7227,
"Corrosion of Aluminum A l l o y s by Flowing High
Temperature Water," Argonne National Laboratory,
January 1967.
Acknow1edgement
This paper was prepared with the support of the

U. S. Energy Research and Development Administration.
RECEIVED September 1,
1978.

8
The Role of Water in Atmospheric Corrosion
P. B. P. PHIPPS and D . W . R I C E
I B M Corporation, San Jose, CA 95193
This paper is divided into three parts. The first

part reviews several types of measurements which we
have made on atmospheric corrosion. These are intended
to provide a s e l f - c o n s i s t e n t set of data from which
generalization can be made. Differences between atmospheric corrosion and dry oxidation become apparent. The
dominant r o l e played by r e l a t i v e humidity in aggravating
atmospheric corrosion is remarkably widespread.
This
fact focuses our attention on the second part -- water
adsorption. Experiments on water adsorption as it
relates to atmospheric corrosion are described and, t o gether with published data suggest important g e n e r a l i zations regarding the adsorbed aqueous medium. In the
t h i r d part the data on atmospheric corrosion presented
in part one is viewed from the perspective of the
adsorbed aqueous phase of part two. Many observations
received a d i r e c t explanation. The value and l i m i t a tions of measurement techniques such as weight gain,
ellipsometry, surface a n a l y s i s , and bulk electrochemi s t r y can be seen in perspective.
0-8412-0471-3/79/47-089-235$06.75/0
1979 American C h e m i c a l Society

CORROSION CHEMISTRY
236
1.0
O b s e r v a t i o n s on A t m o s p h e r i c
Corrosion
1.1 The T e s t Atmosphere. Measurements o f t h e

r e s p o n s e o f m e t a l s t o t h e c o r r o s i v e atmospheres w h i c h
t h e y must w i t h s t a n d in a p p l i c a t i o n s a r e o f g r e a t p r a c t i c a l value.
I n t e s t i n g t h e s e r e s p o n s e s we have two
c o u r s e s , f i e l d e x p o s u r e and e x p o s u r e t o a s y n t h e t i c
t e s t c o n d i t i o n . F i e l d e x p o s u r e has s e v e r a l l i m i t a t i o n s .
I t is s l o w , t h e sample o f t h e e n v i r o n m e n t is v e r y s m a l l
and p o o r l y d e f i n e d .
Laboratory t e s t i n g solves these
p r o b l e m s . I t c a n be a c c e l e r a t e d , and w e l l d e f i n e d .
On
the o t h e r hand i t is n o t o b v i o u s t h a t any s i n g l e gas
m i x t u r e c a n r e p r e s e n t t h e r e s p o n s e o f many m e t a l s t o
varied f i e l d conditions. C e r t a i n l y , the acceleration
f a c t o r s c a n n o t be p r e d i c t e d w i t h o u t much p r i o r k n o w l edge o f s e n s i t i v i t i e s t o gas c o n c e n t r a t i o n s , and temp e r a t u r e s and t h e p r o b a b i l i t
t i o n s . We have s e l e c t e
the s t a t i s t i c s o f t h o s e p o l l u t a n t s (1_) , w h i c h m i g h t
cause c o r r o s i o n . The t e s t c o n d i t i o n s , g i v e n in T a b l e I ,
a r e c h a r a c t e r i s t i c o f h e a v i l y p o l l u t e d urban atmosp h e r e s . A t t e n t i o n has been g i v e n t o m e a s u r i n g t h e
c o r r o s i o n by s e n s i t i v e t e c h n i q u e s r a t h e r t h a n i n c r e a s ing t h e s e v e r i t y o f the t e s t t o unreasonable extremes.
We b e l i e v e t h a t t h e d e f i n i t i o n o f t h i s t e s t is a p r e r e q u i s i t e t o r a t i o n a l i z a t i o n o f atmospheric c o r r o s i o n
responses.
1.2 C o r r o s i o n Response. The r e s p o n s e s o f m e t a l s
t o t h i s t e s t have been measured by s e v e r a l methods. A
b r i e f s u r v e y w h i c h f o l l o w s forms a s e l f - c o n s i s t e n t
b a s i s o f some g e n e r a l i z a t i o n s on a t m o s p h e r i c c o r r o s i o n .
U n l e s s s t a t e d o t h e r w i s e , t h e examples w i l l be o f t h e
c o r r o s i o n o f an a l l o y NisoFe20I n some c a s e s w e i g h t g a i n c a n be used t o m o n i t o r
a t t a c k . F i g u r e 1 shows, f o r example, t h e r a t e o f
w e i g h t g a i n o f a f o i l o f NigQFe2Q
function of the
s u l f u r d i o x i d e l e v e l in o u r gas m i x t u r e w i t h a l l o t h e r
gases c o n s t a n t .
T h i s t e s t was c o n d u c t e d at s e v e r a l
relative humidities.
I t is s t r i k i n g t h a t r e d u c i n g t h e
w a t e r v a p o r p r e s s u r e by a f a c t o r o f two r e d u c e s t h e
r a t e o f a t t a c k a s much as r e d u c i n g t h e s u l f u r d i o x i d e
p r e s s u r e a f a c t o r o f t w e n t y . I t is found t h a t most o f
t h e e f f e c t o f t e m p e r a t u r e on c o r r o s i o n is d e s c r i b e d by
the t e m p e r a t u r e dependence o f w a t e r v a p o r p r e s s u r e c o n t a i n e d in t h e RH. T h i s g r a p h i m p l i e s l i n e a r k i n e t i c s
w h i c h a r e d e m o n s t r a t e d in F i g u r e 2. Here, t h e c o r r o s i o n p r o d u c t t h i c k n e s s was measured by e l l i p s o m e t r y and
w e i g h t change, and t h e c o m p o s i t i o n was shown t o be
a

PHipps
A N D RICE
Water in Atmospheric
Table I
Accelerated reference
atmosphere t e s t
TC
H0
25
N0
480 p p b
8055 RH
so
310 p p b
170 p p b
3
HS
15 p p b
C 1
4.0
Corrosion
3 ppb
r-
Figure 1.
Weight gain of Ni Fe o
80
foil as a function of
pS0
and RH

238

8.
PHiPPS A N D R I C E
239
Corrosion
(NiFe) SO/j'IÔ by xray d i f f r a c t i o n . The two types of

measurement can be compared by using published density
and r e f r a c t i v e index. We believe that the discrepancy
between the two may be an error in the ellipsometry
due to the serious roughening of the surface. In our
experience atmospheric corrosion almost always leads
to s u f f i c i e n t roughening to a f f e c t e l l i p s o m e t r i c data.
This roughening must be taken into account in any
model of the corrosion process.
Direct measurement of roughening has proved to be
a s e n s i t i v e monitor of the corrosion of t h i n f i l m s .
This is because the i n i t i a l condition of vapor deposited
or e l e c t r o p l a t e d films can be very smooth. A semiquant i t a t i v e measure of roughness is provided by the intens i t y of the l i g h t r e f l e c t e d by a sample examined under
a microscope with dark f i e l d i l l u m i n a t i o n . Data taken
by t h i s technique is show in Figur 3
Th
d
dependence of attac
Roughening is much mor
hig
Chromium and aluminum are r e s i s t a n t to atmospheric
corrosion i n d i v i d u a l l y but when porous chromium in i n t i mate contact with aluminum is exposed to high humidities
substantial corrosion occurs at the i n t e r f a c e of the two
materials. This is i l l u s t r a t e d by the roughening data
of Figure 4. Auger electron spectroscopy shows 0, S
CI -- a l l varying in quantity with RH (Figure 5 ) . ESCA
has shown SOf, SO3, and perhaps S2O3". Infra red adsorpt i o n has enabled us to i d e n t i f y hydrated s u l f a t e ,
n i t r a t e , n i t r i t e (Figure 6). Besides these reduced
anions, highly oxidized species such as Co^+ have been
detected.
f
1.3
Summary of Atmospheric Corrosion Data. From
the raw data we can draw several s a l i e n t points.
(i) D i f f e r e n t measurements reveal d i f f e r e n t
aspects of a complex phenomenon.
( i i ) Several phases are often (3_) present in
r e a l atmospheric corrosion products.
A wide
range of oxidation l e v e l s is present on samples
at one time.
(iii)
Structures containing d i s s i m i l a r metals
show galvanic i n t e r a c t i o n s q u a l i t a t i v e l y l i k e
those seen in aqueous environments.
(iv) The rough morphology and the mixed products suggest that models of the r a t e - l i m i t i n g
steps w i l l be more complex than those of, e.g.,
t a r n i s h i n g . As is true of low temperature
oxidation (2^) , k i n e t i c studies of the rate of
growth contain too few parameters to resolve these
complexities.
Mechanistic experiments must be designed.

240
CORROSION
CHEMISTRY
Time Days
Figure S.
Roughening attributable to atmospheric corrosion measured by light

scattering. Corrosion of plated NiFe films in reference test.

p f f l p p s A N D RICE
Corrosion
i50r
/bb%
75% RH /
/
/
/
RH
//
/
Cr Thin Films on Glass
Cr Thin Films on AI
//
//
. 75% RH
...*.*.*-"-'- 55% RH
^^S.CS.iS^.'-i:^
2
Figure 4.
- 3 0 % RH
3
Time Days
Galvanic corrosion of aluminumincontact with chromium

242
CORROSION CHEMISTRY
Unexposed
A 2 0 % R.H. 72 h.
4 5 % R.H.
6 2 % R.H.
7 5 % R.H.
150
200
Depth
Figure 5.
Auger electron spectroscopy of cobalt exposed to various atmospheres;

cobalt corrosion
Wavelength (Microns)
4
_J
3500
3000
2500
10
II
II
2000
1800
1600
1400
1200
1000
12
L_
L_
800
Frequency (cm )
-1
Figure 6.
IR adsorption of corrosion products formed on NiFe in this "standard

test atmosphere"

8.
PHiPPS A N D R I C E
Corrosion
243
(v)
RH is a dominant v a r i a b l e in many examples.
A l t h o u g h t h e RH at w h i c h c o r r o s i o n is n e g l i g i b l e
depends on t h e o t h e r gases p r e s e n t and t h e s e n s i t i v i t y o f d e t e c t i o n , d i f f e r e n t a u t h o r s see t h e
same t r e n d . T h i s is b r o u g h t o u t by comparing some
p u b l i s h e d " c r i t i c a l r e l a t i v e h u m i d i t i e s " at w h i c h
c o r r o s i o n is m i n i m a l , see T a b l e I I . S e v e r a l
workers
5_, 6_) have r e p o r t e d e l e c t r o c h e m i c a l
c u r r e n t s between d i s s i m i l a r m e t a l s , c o n n e c t e d by
a d s o r b e d w a t e r . I t is i n f e r r e d t h a t t h i s c u r r e n t
between p a r t i c u l a r m e t a l s at a s i n g l e p o t e n t i a l
r e p r e s e n t s "the t i m e o f w e t n e s s " , and t h i s w i l l be
a measure o f t h e amount o f ( g a l v a n i c ) c o r r o s i o n
between h e t e r o g e n i t i e s on a s i n g l e m e t a l o r between any d i s s i m i l a r m e t a l s exposed t o t h e same
atmosphere.
Thi constitute
extrem
statement
of the g e n e r a l i t
a b l e in many c a s e
atmospheri
We m i g h t summarize t h a t t h e RH is g e n e r a l l y
a dominant f a c t o r . F o r most m e t a l s , o x i d e s a r e
a l w a y s p r e s e n t on t h e s u r f a c e e x c e p t at t h e b o t tom o f g r o w i n g p i t s , b u t no c o r r o s i o n is d e t e c t e d
below 15% RH and most m e t a l s do c o r r o d e above 75%
RH r e g a r d l e s s o f t h e p a r t i c u l a r gas c o n c e n t r a t i o n s
o r s p e c i e s in t h e a c c e l e r a t e d a t m o s p h e r i c t e s t .
T h i s f o c u s e s a t t e n t i o n on t h e q u e s t i o n o f what is
c h a n g i n g so d r a m a t i c a l l y when t h e RH changes a f a c t o r
of f i v e t i m e s . C l e a r l y , t h e q u a n t i t y o f a d s o r b e d w a t e r
is i n c r e a s i n g b u t , at 15% RH (3 mm at 25C), a s i g n i f i c a n t q u a n t i t y o f a d s o r b e d w a t e r is p r e s e n t and at 75%
RH, by d e f i n i t i o n , t h e e q u i l i b r i u m q u a n t i t y cannot be
so g r e a t t h a t t h e w a t e r has b u l k p r o p e r t i e s .
(Bulk
w a t e r would e v a p o r a t e i f t h e RH is l e s s t h a n 100%!)
Water a d s o r p t i o n d a t a on c o r r o d i n g m e t a l s s u r f a c e s is
n o t a v a i l a b l e . Water a d s o r p t i o n c o m p r i s e s t h e s u b j e c t
of t h e second s e c t i o n o f t h i s p a p e r .
2.0
Water A d s o r p t i o n
Two t y p e s o f w a t e r a d s o r p t i o n e x p e r i m e n t s a r e
r e l e v a n t t o o u r a n a l y s i s . As an example o f one t y p e ,
t h i n f i l m s o f h i g h p u r i t y aluminum, d e p o s i t e d at 10"^
t o r r , show changes in work f u n c t i o n (1) and LEED p a t t e r n (S) and g a i n mass (9J due t o e x p o s u r e t o 10~ t o r r
sec o f H 0. T h i s d a t a can be a t t r i b u t e d t o M-OH d i p o l e s
o

244
CORROSION
CHEMISTRY
Table II C r i t i c a l r e l a t i v e humidities
ppm
Metal
by Volume
C r i t . RH %
Ref.
Fe
3000
100
200
100
0.5
0.1
75
65
85
>90
80
80
1
3
5
5
6
7
Cu
3000
100
0.5
0.1
0.1
60
63
1
2,3
90
Ni
1000
70
Al
3000
1000
300
0
0.1
82
52
52
85
90
1
4
4
4
7
References
1. Sanyal, B. and Bhadwer, D., J. S c i . Ind. Res. India
(1957) 18A, 69.
2. Vernon, W.H., Trans. Far. Soc. (1935) 3J_, 1668.
3. Vernon, W.H., J. Electrochem. Soc. (1933) 64, 31.
4. A z i z , P.M. and Godard, H.P., Corrosion (1957) 1_5, 39.
5. S k o r c h e l l e t t i , V.V. and Tukachinsky, S.E., J. App.
Chem. USSR (1953) 26, 27, (1955) 28, 65.
6. Clarke, S.G. and Longhurst, E.E., J. Applied Chem.
(1961)
435.
7. Sydberger, T. and Vanneberg, N.G., Corr. S c i . (1972)
12:, 775.
8. Duncan, J.R. and Spedding, D.J., Corr. S c i . (1973)
1J3, 993.

8.
PHIPPS A N D RICE
Corrosion
245
o r i e n t e d on t h e s u r f a c e . S i m i l a r r e s u l t s have been
r e p o r t e d f o r c l e a v e d A l (10J , f o r Au (U) , W (V2) , P t
(13) , Fe (14) . I n a second type o f e x p e r i m e n t , powdered
m e t a l o x i d e s w i t h h i g h c a t a l y t i c a c t i v i t y and s u r f a c e
a r e a a r e exposed t o w a t e r and an a d s o r p t i o n i s o t h e r m is
plotted.
I n f r a r e d a d s o r p t i o n (15,1_), NMR r e l a x a t i o n
(IZ'UL'ID
d i e l e c t r i c d i s p e r s i o n (2,2J_,^2) may be
measured on t h e s u b s t a n t i a l number o f m o l e c u l e s a d sorbed on t h e s u b s t a n t i a l a r e a . U n f o r t u n a t e l y , i t is
d i f f i c u l t t o apply e i t h e r o f these f i e l d s o f i n v e s t i g a t i o n t o the e l u c i d a t i o n o f atmospheric c o r r o s i o n .
The d e f i n i t i o n o f t h e powder s u r f a c e s t e n d s t o be
in terms o f t h e p r o c e s s f o r making i t (23). T h i s
l i m i t s i n t e r p r e t a t i o n o f t h e i r p r o p e r t i e s and a l s o
l i m i t s g e n e r a l i z a t i o n o f p r o p e r t i e s t o surfaces which
have been g e n e r a t e d
v e r s e l y , t h e LEED, Auge
e m i s s i o n p r o p e r t i e s , e t c . , a r e measured on f r e s h s u r f a c e s in UHV, because i n t e r p r e t a t i o n is d i f f i c u l t f o r
more complex c o n f i g u r a t i o n s and because e x p e r i e n c e has
shown t h a t t h e s e p r o p e r t i e s a r e p r o f o u n d l y m o d i f i e d and
c o n f u s e d by e x p o s u r e t o r e a l atmospheres.
The e x p e r i m e n t d e s c r i b e d below is an a t t e m p t t o
b r i d g e t h i s gap. S u r f a c e s r e l e v a n t t o a t m o s p h e r i c
c o r r o s i o n were p r e p a r e d from c l e a n m e t a l s u r f a c e s by
r e a c t i o n w i t h w a t e r v a p o r under c l e a n c o n d i t i o n s . The
p r o p e r t i e s measured w a t e r a d s o r p t i o n c h a r a c t e r i s t i c s
were s e l e c t e d because t h e y were b e l i e v e d t o have a
major and d i r e c t a p p l i c a t i o n t o a t m o s p h e r i c c o r r o s i o n .
o
2.1 Water A d s o r p t i o n E x p e r i m e n t s . The o b j e c t i v e s

were t o measure w a t e r a d s o r p t i o n i s o t h e r m s on s u r f a c e s
w h i c h were w e l l d e f i n e d in terms o f t h e i r p r e p a r a t i o n
and a l s o r e l e v a n t t o a t m o s p h e r i c c o r r o s i o n .
The q u a n t i t y o f w a t e r a d s o r b e d on t h e a p p r o p r i a t e
m e t a l s u r f a c e was measured by means o f a p i e z o e l e c t r i c
q u a r t z m i c r o b a l a n c e (24_) . W i t h s u i t a b l y c u t c r y s t a l s
and good t e m p e r a t u r e c o n t r o l , i t was p o s s i b l e t o meas u r e a d s o r p t i o n c o r r e s p o n d i n g t o c o v e r a g e by a f r a c t i o n
o f a monolayer.
The sequence o f o p e r a t i o n s l e a d i n g t o a d s o r p t i o n
d a t a d e s c r i b e d h e r e c a n be f o l l o w e d by r e f e r e n c e t o
Figure 7 .
( i ) A t h e r m o s t a t e d q u a r t z c r y s t a l was c o a t e d
w i t h N i F e by e l e c t r o n beam e v a p o r a t i o n in an o i l f r e e system at a p r e s s u r e o f l e s s t h a n 10-8 t o r r ,
so t h a t t h e r a t e o f i n c i d e n c e o f m e t a l atoms was
at l e a s t a t h o u s a n d t i m e s t h a t o f o t h e r s p e c i e s .

246
Figure 7.
Mass changes as a function of water pressure; adsorption of water on

Ni Fe o film at 25 C
80

8. PHiPPS A N D R I C E
Corrosion
(ii)
The c l e a n m e t a l s u r f a c e was now exposed t o
water vapor.
T h i s was o b t a i n e d from w a t e r w h i c h
had been r e p e a t e d l y d i s t i l l e d in t h e UHV chamber.
The p r e s s u r e o f w a t e r was d e t e r m i n e d by t h e temp e r a t u r e o f t h i s w a t e r . T o t a l gas p r e s s u r eint h e
vacuum system was m o n i t o r e d by an i o n gauge, w h i c h
was n o t o p e r a t e d c o n t i n u o u s l y , and by a t h e r m a l
c o n d u c t i v i t y gauge. A f t e r a b r i e f t r a n s i e n t t h e
frequency o f o s c i l l a t i o n s decreased t o a steady
v a l u e i n d i c a t i n g t h a t t h e mass o f t h e q u a r t z
c r y s t a l s u r f a c e had i n c r e a s e d due t o r e a c t i o n w i t h
t h e w a t e r . An e f f e c t was o b s e r v e d f o r p r e s s u r e a s
low as 10"" t o r r .
(iii)
The m e t a l f i l m was now exposed t o a
g r e a t e r w a t e r v a p o r p r e s s u r e and t h e a d s o r p t i o n
was m o n i t o r e d u n t i l
p r o c e d u r e was r e p e a t e
w a t e r v a p o r p r e s s u r e up t o ~ 10 t o r r .
_
(iv)
The w a t e r v a p o r was pumped o f f t o 10""
t o r r , b u t t h e mass o f t h e f i l m d i d n o t r e v e r t t o
i t s o r i g i n a l v a l u e , p a r t o f the adsorbed water
c o u l d n o t be d e s o r b e d at t h i s t e m p e r a t u r e and
pressure.
(v) The w a t e r p r e s s u r e was r e t u r n e d t o 11 t o r r ,
and t h e f i l m was l e f t t o e q u i l i b r a t e f o r 72 h o u r s .
(vi)
The w a t e r a d s o r p t i o n c u r v e was now meas u r e d on t h e r e a c t e d s u r f a c e . The i r r e v e r s i b l e
a d s o r p t i o n w h i c h o c c u r r e d d u r i n g measurement was
n e g l i g i b l e compared w i t h t h a t w h i c h had t a k e n
p l a c e d u r i n g t h i s 72 h o u r s o f c o n d i t i o n i n gatt h e
highest pressure.
R e v e r s i b l e a d s o r p t i o n d a t a was
recorded.
( I tisi n t e r e s t i n g t o n o t e t h a t a h i g h
p r e s s u r e o f hydrogen d e v e l o p e d in t h e vacuum
chamber a s i n d i c a t e d b y a gas w i t h a v e r y h i g h
t h e r m a l c o n d u c t i v i t y w h i c h c o u l d n o t be s o r p t i o n
pumped o r cryopumped b u t c o u l d be removed by
t i t a n i u m s u b l i m a t i o n . T h i s was p r o b a b l y formed
by r e a c t i o n o f t h e w a t e r v a p o r w i t h t h e f r e s h l y
d e p o s i t e d m e t a l on t h e w a l l s o f t h e chamber.)
(vii)
The f i l m was now exposed t o w a t e r v a p o r at
11 t o r r f o r a f u r t h e r 100 h o u r s .
The f r e q u e n c y
decreased monotonically.
(viii)
Dry a i r was i n t r o d u c e d . The c r y s t a l
showed t h a t no mass change o c c u r r e d .
The a d s o r p t i o n c u r v e was remeasured.
The e q u i l i b r i u m mass changes a r e p l o t t e d in
F i g u r e 8 on t h e b a s i s o f t h e BET model (25) . From
t h i s model we d e r i v e t h e a c t i v a t i o n e n t h a l p y f o r
w a t e r a d s o r p t i o n and t h e a r e a o f t h e f i l m .
These
6
American Chemical
Society Ubory
1155 16th st a w.
In Corrosion
Chemistry;0.
Brubaker,
G., et al.;
Washington,
C. 20036
248
Figure 8.
Adsorption isotherms plotted on the basis of the BET model

8.
PHipps
A N D RICE
Water
in
Atmospheric
Corrosion
249
p a r a m e t e r s a r e shown in T a b l e I I I as t h e r a t i o o f
t h e t r u e a r e a t o t h e a p p a r e n t a r e a . The q u a n t i t y
o f w a t e r a d s o r b e d is p l o t t e d in u n i t s o f l a y e r s o f
w a t e r on t h e b a s i s o f t h i s a n a l y s i s ( F i g u r e 9).
(ix)
F i n a l l y , s e v e r a l m e t a l s were d e p o s i t e d on
q u a r t z c r y s t a l s and t h e w a t e r a d s o r p t i o n was meas u r e d in l a b o r a t o r y a i r at c o n t r o l l e d r e l a t i v e
humidities.
These measurements were i n t e n d e d t o r e p r e s e n t
a more p r a c t i c a l degree o f c l e a n l i n e s s t h a n t h e
s u r f a c e p r e p a r e d in UHV.
Some d a t a a r e shown in
F i g u r e 10 and 11, and r e s u l t s f o r a number o f
m e t a l s a r e shown in T a b l e I I I w h i c h compares t h e s e
measurements w i t h p u b l i s h e d d a t a .
2.2
D i s c u s s i o n . The c l e a n f i l m o f m e t a l ^ r e a c t s
r a p i d l y w i t h water vapo
produce H2 and in t h
hydroxide/oxide.
(Evidence on t h e n a t u r e o f t h i s r e a c t i o n p r o d u c t is r e v i e w e d below.) The r e a c t i o n is
effectively irreversible.
The f r e q u e n c y t r a n s i e n t
o b s e r v e d when t h e m e t a l was f i r s t exposed is p r o b a b l y
due t o a t h e r m a l g r a d i e n t in t h e q u a r t z a s s o c i a t e d w i t h
t h i s r a p i d h i g h l y e x o t h e r m i c r e a c t i o n . Subsequent
w a t e r is a d s o r b e d ( r e v e r s i b l y ) on t o p o f t h i s r e a c t i o n
p r o d u c t (~ 1 monolayer at 25% RH, ~ 2 at 50% RH). T h i s
a d s o r b e d w a t e r r e a c t s w i t h t h e s u b s t r a t e m e t a l much
more s l o w l y t h a n t h e i n i t i a l r e a c t i o n . (One monolayer
r e a c t i n g in s i x t y h o u r s at 10 t o r r H2O.)
Dramatic
r e d u c t i o n s in r e a c t i o n r a t e a f t e r t h e f o r m a t i o n o f t h e
f i r s t monolayer have been r e p o r t e d from o b s e r v a t i o n s in
s o l u t i o n (2j5) . I t has been shown t h a t w a t e r is n e c e s s a r y f o r t h i s p a s s i v a t i o n o f n i c k e l (27). As t h e compound f i l m grows t h i c k e r , t h e a c t i v a t i o n energy f o r
w a t e r a d s o r p t i o n does n o t change b u t t h e a r e a i n c r e a s e s .
T h i s is c o n s i s t e n t w i t h t h e l i n e a r growth r a t e .
Rea c t i o n r a t e is l i m i t e d by t h e monolayer. T h i s is
c o n s t a n t l y , but s l o w l y , regenerated.
The q u a n t i t y o f
a d s o r b e d w a t e r i n c r e a s e s w i t h t i m e at c o n s t a n t RH
because t h e a r e a o f porous h y d r o x i d e i n c r e a s e s w i t h
time.
The newly g e n e r a t e d s u r f a c e is a r e l a t i v e l y
c l e a n ( r e p r o d u c i b l e ) a d s o r b e n t (perhaps t h i s a c c o u n t s
f o r t h e s i m i l a r a d s o r p t i o n on f i l m s exposed t o l a b o r a t o r y a i r and t h o s e p r e p a r e d in an u l t r a c l e a n e n v i r o n ment) .
We t u r n now t o d i s c u s s f i r s t t h e e v i d e n c e on t h e
nature of the adsorbing s u r f a c e , then the p r o p e r t i e s
o f t h e a d s o r b e d aqueous phase. T h i s l e a d s us t o a
model f o r a t m o s p h e r i c c o r r o s i o n .

250
Table III
Water adsorption parameters
Heats of Adsorption of Water at High Coverage

Adsorbent
I s o s t e r i c : Heat
kcals/mole
Roughness
BET
Ref.
Au
11 .84
12
11.5
2.5
6
10
1,2
3
4
Fe
11 .72
13.2
3
2
2
3
Co
11.7
2.9
Ni
11.7
Pt
10.1-12.4
11.3 13.3
6
8
Sn
Ni Fe
12.75
12.44
11.74
3.5
5.4
1
2
Fe Cr
11.73
Fe Ni Cr
13
2.2
A l 0 OH
12+0.5
F e
12.8
11.6
10
23
Ni 0
References
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
This work, UHV.

This work, a i r exposed.
Bowder, F.P. and Throssel, W.R., Proc. Roy. Soc.
(1951) A209, 297.
Thomas, J.H.,III and Sharma, S.P., J. Vac. S c i .
Tech. (1976) V3, 549.
Armbruster, M.H., J. Am. Chem. Soc. (1966) 68,
1342.
A l l e n , K.W., J. Chem Soc. A (1971), 3028.
Garner, R.L., Thesis Texas Tech. C o l l . (1965).
Cole, H.D.F., Thesis University of Texas (1964).
Zettlemoyer, A.C. and McCafferty, ., Phys.
Chem. NF (1969) 64, 41.
Cronin, C.L., Thesis Lehigh University (1976).

pmpps A N D R I C E
0.1
0.2
0.3
0.4
Corrosion
0.5
0.6
0.7
Relative Humidity P/Po

Figure 9.
Water adsorptioninmonolayers on Permalloyinair

252
Figure 10.
Water adsorption on gold film

prapps A N D RICE
Corrosion
10 r
Relative Humidity P/Po

Figure 11.
Water adsorption on several metals exposed to air

254
2.3 The S o l i d A d s o r b e n t . I n c h a r a c t e r i z i n g t h e
l a y e r on w h i c h a d s o r p t i o n o f w a t e r t a k e s p l a c e r e v e r s i b l y , we make t h e f o l l o w i n g o b s e r v a t i o n s :
(i)
The i n i t i a l r e a c t i o n o f a c l e a n m e t a l
s u r f a c e w i t h w a t e r v a p o r is e f f e c t i v e l y i r r e v e r
s i b l e and i n v o l v e s d i s s o c i a t i o n . T h i s is s u p p o r t e d
by t h e e v o l u t i o n o f h y d r o g e n , t h e r a p i d e x o t h e r m i c
r e a c t i o n , and p u b l i s h e d d a t a f o r s e v e r a l m e t a l s
(7,8,9,10, .
(ii)
The i n i t i a l r e a c t i o n p r o d u c t p r o t e c t s t h e
m e t a l from f u r t h e r a t t a c k .
By t h e word " p r o t e c t , "
we a r e c o n t r a s t i n g t h e r a t e o f f o r m a t i o n o f t h e
i n i t i a l i r r e v e r s i b l y bound l a y e r w i t h i n ~ 10"** t o r r
seconds w i t h t h e subsequent growth o f an i r r e v e r
s i b l y bound monolayer in ~ 60 h o u r s at 11 t o r r =
2.5 10*> t o r r seconds
Auger e l e c t r o n s p e c t r o
scopy
and 1_6
be r e p r e s e n t e d a
further attack.
D i r e c t e v i d e n c e o f hydrogen b e i n g
p r e s e n t in t h e p a s s i v e f i l m formed in s o l u t i o n was
p r o v i d e d by mass s p e c t r o m e t r y (30).
Electron
d i f f r a c t i o n (2,29) has shown t h a t t h e p r o t e c t i v e
s u r f a c e l a y e r s w h i c h form on i r o n w h i c h has been
a i r o x i d i z e d o r p a s s i v a t e d in s o l u t i o n a r e s u r p r i s
i n g l y s i m i l a r . The s t r u c t u r e s a r e based on t h e
c u b i c c l o s e packed oxygen l a t t i c e o f Fe 0 OH, o r
Fe304.
The d e t a i l s o f t h e p r o c e s s e s by w h i c h p a r t i
c u l a r monolayers l i m i t t h e k i n e t i c s o f metal
o x i d a t i o n and " o x i d e " d i s s o l u t i o n have been t h e
s u b j e c t o f much i n v e s t i g a t i o n . (See r e f e r e n c e s
on p a s s i v i t y , (2_6 and 28) .) We do n o t a t t e m p t t o
review o r develop these studies here, but t o
e s t a b l i s h a c o n n e c t i o n between a t m o s p h e r i c c o r r o
s i o n and t h e r e l a t i v e l y w e l l s t u d i e d d i s c i p l i n e s
o f aqueous c o r r o s i o n and d r y o x i d a t i o n .
(iii)
The c r i t i c a l i n t e r a c t i o n w h i c h b i n d s
w a t e r when i t is o s t e n s i b l y a d s o r b e d on a
c o r r o d i n g m e t a l is t h e i n t e r a c t i o n w i t h an o x i d e
o r o x y h y d r o x i d e . The o b s e r v a t i o n o f s i m i l a r
a d s o r p t i o n c h a r a c t e r i s t i c s on many m e t a l s ( a f t e r
t h e i n i t i a l i r r e v e r s i b l e r e a c t i o n ) and on many
o x i d e s s u p p o r t s t h i s (Table I I I ) . The g e n e r a l i
z a t i o n is r e i n f o r c e d by t h e o b s e r v a t i o n t h a t i f
e x p o s u r e is p r o l o n g e d t h e a r e a o f t h e a d s o r b e n t
i n c r e a s e s , b u t t h e o t h e r c h a r a c t e r i s t i c s do n o t
change. A p p a r e n t l y , t h e g r o w i n g l a y e r is r e l a
t i v e l y p o r o u s , and t h e p r o t e c t i o n is p r o b a b l y due
to the l a y e r adjacent t o the metal. This follows
from t h e i n c r e a s i n g a r e a and t h e c o n s t a n t r a t e o f
growth.

8.
PHipps A N D RICE
255
Corrosion
This discussion of the s o l i d phase on which the

water is adsorbed has brought us to a conclusion which
is important f o r our subsequent examination of the
aqueous adsorbed phase. The water which is not ( i r r e versibly) decomposed is adsorbed on an oxyhydroxide
whose exact nature has only a minor e f f e c t on the
adsorption phenomena. There is substantial l i t e r a t u r e
on the properties of adsorbents on t h i s type of surface.
A review of t h i s l i t e r a t u r e allows us to propose the
following generalizations concerning the aqueous phase
in atmospheric corrosion.
2.4 The Aqueous Adsorbate. The aqueous phase
acts as (i) solvent, ( i i ) d i e l e c t r i c and ( i i i ) transport vehicle and w i l l be discussed under these three
topics.
(i) The solvatio
and hydroxide is of major importance in atmospheric corrosion but relvent data is scarce and
theories which might support extrapolation from
other measurements are d i f f i c u l t to apply to
solutions in adsorbed water.
Consideration of the parameters of the gases
given below
HCl
Gases
H0
N0
373
294
263
188
Heat of evap.
kcal/mole
10.5
5.1
3.8
Pressure in a i r
atmospheres
"
io-
so
IO"
IO"
90
3.2
IO"
shows that, generally, water w i l l be adsorbed mul

t i l a y e r s and other gases, i f there were no water,
to f r a c t i o n s of monolayers. (In the BET model the
heat of adsorption of layers a f t e r the f i r s t is
equal to H .)
Expressions have been developed to
describe the adsorption of mixed gases on the
basis of the BET or Langmuir models (3V) . I f the
gases i n t e r a c t l i t t l e , the observations can be
f i t t e d to the theory, e.g., N2/ and O2 on T1O2
(32); but with greater i n t e r a c t i o n , e.g., C2H5 and
CO2 on Cr 03 (3_3) agreement is poor. The layer
v

256
CORROSION
CHEMISTRY
d i p o l e s , t h e a m b i d e n t a t e c h a r a c t e r o f SO3 and NO3,

and t h e s t r o n g i n t e r a c t i o n w i t h b u l k H 0 l e a d us
t o doubt t h e use o f t h e s e a d s o r p t i o n models. A l though d e t a i l e d t r e a t m e n t s o f i n t e r a c t i o n s and o f
aqueous s o l u b i l i t y have been g i v e n , t h e y r e q u i r e
more knowledge o f t h e s o l v e n t p r o p e r t i e s t h a n is
a v a i l a b l e f o r a d s o r b e d w a t e r on o x i d e .
I t is p r o p o s e d t h a t a q u a l i t a t i v e a c c o u n t c a n
be r a t i o n a l i z e d on t h e b a s i s o f t h e s t r e n g t h o f
the i n t e r a c t i o n s between s o l v e n t , s o l u t e , and
a d s o r b e n t . As an example o f weak i n t e r a c t i o n s ,
the c o v e r a g e o f n i t r o g e n on a r g o n on t i t a n i u m
d i o x i d e is r e d u c e d by ~ 0.2 l a y e r s i f one l a y e r o f
w a t e r is a d s o r b e d and a f u r t h e r 0.1 l a y e r i f f o u r
l a y e r s o f w a t e r a r e a d s o r b e d ( 3 4 ) . The i s o t h e r m
a f t e r f o u r l a y e r s o f w a t e r p r o v e s t o be v e r y s i m i lar to that of nitroge
t i v e b e h a v i o r resemble
d e v i a t i o n s . The w a t e r - w a t e r and w a t e r - o x i d e
i n t e r a c t i o n s , being stronger than the argon-oxide o r
a r g o n - a r g o n o r a r g o n - w a t e r , t h e a r g o n p r e s s u r e is
r a i s e d o v e r t h a t o f an i d e a l s o l u t i o n , i . e . , t h e
q u a n t i t y o f a r g o n a d s o r b e d is r e d u c e d at a g i v e n
p r e s s u r e . The more p o l a r i z a b l e xenon and k r y p t o n
have been r e p o r t e d t o form c l a t h r a t e s w i t h a d s o r b e d i c e (36). An example o f a s t r o n g l y i n t e r a c t i v e system may be t a k e n from t h e l i t e r a t u r e o f
c a t a l y s i s . Water a d s o r b e d on s i l i c a ( o r alumina)
behaves as a B r o n s t e d a c i d (37) and c a n be
t i t r a t e d w i t h ammonia. The c o n c e n t r a t i o n s o f
a d s o r b e d ammonia and ammonium c a n be measured
s p e c t r o s c o p i c a l l y (38_) .
(ii)
D i e l e c t r i c p r o p e r t i e s o f adsorbed water The s o l v a t i o n o f g a s e s , m e t a l i o n s , p r o t o n s and
h y d r o x i d e i o n s is c r u c i a l in e l e c t r o c h e m i c a l c o r r o s i o n . The d e t a i l s o f t h e h y d r a t i o n s h e a t h in t h e s e
a d s o r b e d l a y e r s cannot be g i v e n , b u t a m i c r o s c o p i c
p a r a m e t e r is p r o v i d e d by measurements o f t h e
d i e l e c t r i c c o n s t a n t o f a d s o r b e d l a y e r s . The d i e l e c t r i c c o n s t a n t d i s p e r s i o n o f a d s o r b e d w a t e r has
been measured on s e v e r a l o x i d e powders (20,21,23).
I t a p p e a r s t h a t t h e f i r s t l a y e r is r e l a t i v e l y
u n p o l a r i z a b l e and t h e d i e l e c t r i c c o n s t a n t in t h e
o r d e r o f t h r e e b u t , w i t h an average o f o n l y two
l a y e r s , t h e d i e l e c t r i c c o n s t a n t was in t h e o r d e r
of t h i r t y f o r a f r e q u e n c y o f 100 Hz. The c h a r a c t e r i s t i c f r e q u e n c y is ~ 1 kHz. E v i d e n c e i n d i c a t e s
c l u s t e r s o f water being heterogeneously d i s t r i b u t e d .
As t h e t h i c k n e s s i n c r e a s e s beyond t h r e e l a y e r s , t h e
c h a r a c t e r i s t i c f r e q u e n c y approaches t h a t o f i c e ,
s u g g e s t i n g a development o f hydrogen b o n d i n g between w a t e r m o l e c u l e s .
2

8.
PHIPPS A N D RICE
Corrosion
257
Measurements of the DC conductivity have been

interpreted to suggest that the d i e l e c t r i c constant increases with thickness and the d i s s o c i a t i o n energy f a l l s from 0.6 eV towards that seen in
the bulk 0.35 eV (39,40).
( i i i ) M o b i l i t y - The f i r s t layer of water is
r e l a t i v e l y immobile. The d i r e c t measurement o f
v i s c o s i t y in t h i n layers has been the subject o f
some controversy, but rheological a b n o r m a l i t i e s
( i f any) do not extend beyond a few molecular d i a meters (4^, 4_2) . NMR measurements have shown that
monolayers of water are oriented on s i l i c a t e and
s i l i c a gel (1J7/18).
Reduced d i f f u s i o n in these
layers is shown~Ey pulsed spin echo NMR (1_9) and
by neutron s c a t t e r i n g (43^) .
Infrared adsorptio
broadening (15,1^6
that water is bound 0 downwards to the HO M. The
l i f e t i m e , and population, of aggregates and hydrat i o n sheaths is strongly affected by the r o t a t i o n a l
freedom of the water molecules. In bulk water t h i s
is r e s t r i c t e d by hydrogen bond breaking. In adsorbed layers the i n t e r a c t i o n with the adsorbate
dominates r e o r i e n t a t i o n for a l l molecules within
six to ten molecular diameters.
2.5
Summary of Water Adsorption. The discussion
of the adsorbed aqueous phase has been drawn from many
f i e l d s and r e c a p i t u l a t i o n may be h e l p f u l . Most metals
adsorb a monolayer of water r a p i d l y and " i r r e v e r s i b l y . "
This i n i t i a l layer reacts slowly in many cases.
Subsequent water adsorption is s i m i l a r for many metals
and oxides. At 20% RH there w i l l be ~ one monolayer,
and at 15% ~ f i v e layers. Corrosive gases w i l l not
form m u l t i m o l e c u l a r layers, but compete with water f o r
the f i r s t " i r r e v e r s i b l e " layer. The "solution" of gas
w i l l be very d i l u t e . There is ample evidence for
strong i n t e r a c t i o n s between adsorbed water and other
adsorbed gases, but a quantitative model is not a v a i l able. The s o l u t i o n and i o n i z a t i o n within t h i n adsorbed
layers w i l l depart strongly from that in bulk water.
This may be seen from the v a r i a t i o n of d i e l e c t r i c constant with thickness of adsorbed water. A monolayer
has a d i e l e c t r i c constant in the order of three, but at
5095 RH we have two o r three layers with a mean d i e l e c t r i c constant in the order of twenty f i v e a medium
l i k e methanol. Ionic mobility w i l l be possible in t h i s
layer, but m o b i l i t i e s may be an order of magnitude l e s s
than those in bulk s o l u t i o n .

258
We now r e t u r n t o d i s c u s s t h e o b s e r v a t i o n s o f atm o s p h e r i c c o r r o s i o n d e s c r i b e d in t h e f i r s t p a r t o f t h i s
paper in terms o f t h e models o f t h e a d s o r b e d phase dev e l o p e d in t h e p r e v i o u s s e c t i o n s .
3.0
The
R o l e o f Water in A t m o s p h e r i c
Corrosion
3.1
General Observations.
We saw t h a t w a t e r v a p o r
p l a y s a dominant r o l e in many a t m o s p h e r i c c o r r o s i o n
p r o c e s s e s ( F i g u r e s 1,3,5), and t h a t t h e r e is an i m p l i c i t
o b s e r v a t i o n t h a t t h e t e m p e r a t u r e dependence o f c o r r o s i o n
may be a p p r o x i m a t e l y r e p r e s e n t e d by t h e v a p o r p r e s s u r e
o f w a t e r ( i . e . , RH is t h e r a t i o n a l v a r i a b l e ) .
These
o b s e r v a t i o n s a r e c o n s i s t e n t w i t h t h e a d s o r p t i o n model
w i t h h i g h r a t e s o f g a l v a n i c c o r r o s i o n o c c u r i n g in t h i c k
l a y e r s o f w a t e r and o n l y s l o w e r o x i d a t i o n o c c u r i n g in
t h e regime o f RH at w h i c
The s i m i l a r dependenc
s e v e r a l r e a c t a n t s is a l s o c o n s i s t e n t w i t h a d s o r p t i o n on
s i m i l a r o x y h y d r o x i d e l a y e r s even though t h e a r e a t e n d s
t o i n c r e a s e . The s i m u l t a n e o u s p r e s e n c e o f s e v e r a l o x i d a t i o n p r o d u c t s in p o r o u s l a y e r s ( F i g u r e s 5 and 6) is
c o n s i s t e n t w i t h t h e inhomogeneous g a l v a n i c r e a c t i o n s .
The p r o c e s s is d i f f e r e n t from t h e g r a d a t i o n o f s t o i c h i ometry n e c e s s a r i l y p r e s e n t in a d h e r e n t p r o t e c t i v e l a y e r s .
D e l i q u e s c e n c e o f t h e p r o d u c t s is e x p e c t e d t o a f f e c t c o r r o s i o n r a t e s and t h e i r dependence on RH c o n s i d e r a b l y
(4_,5^, 1_0/iLi) # t h e w a t e r t h i c k n e s s b e i n g g r e a t l y i n c r e a s e d .
3.2
I n t e r m e d i a t e RH.
A t i n t e r m e d i a t e RH, ~ 40%,
w e i g h t changes a r e m i n o r but r o u g h e n i n g is seen ( F i g u r e
3) and s e n s i t i v e s u r f a c e c h e m i s t r y shows t h a t t h i n l a y e r s
o f c o r r o s i o n p r o d u c t s can be d e t e c t e d ( F i g u r e 4 and 5 ) .
This
r o u g h e n i n g may be a s s o c i a t e d w i t h t h e f a c t t h a t a d s o r p t i o n shows c l u s t e r i n g even on homogeneous s u r f a c e s , and
p r a c t i c a l s u r f a c e s a r e c e r t a i n l y inhomogeneous w i t h
r e s p e c t t o a d s o r p t i o n . The p r e f e r r e d s i t e s f o r a t t a c k
may be r e l a t e d t o t h e s p e c i f i c a d s o r p t i o n s i t e s des c r i b e d f o r SO2 (45,46j and H S (7); t h e y may be s i t e s
where t h e w a t e r a b s o r p t i o n is f a v o r e d ; o r t h e y may be
s i t e s at w h i c h t h e o x i d e is weak. Once c o r r o s i o n is
i n i t i a t e d , d e l i q u e s c e n t c o r r o s i o n p r o d u c t s may a g g r a v a t e
l o c a l a t t a c k (see b e l o w ) .
2
3.3
Low RH.
A t t h o s e s i t e s , and f o r t h o s e c o n d i t i o n s , in w h i c h t h e a v e r a g e t h i c k n e s s is in t h e o r d e r
o f one m o l e c u l e 3 t h e d i e l e c t r i c c o n s t a n t is low and
h y d r a t i o n o f i o n s H *, OH", O2, M ,
SO2-, e t c . , is
4
n+

8.
PHipps A N D R I C E
Corrosion
259
e n e r g e t i c a l l y unfavorable. (Atmospheric corrosion

monitors based on recording galvanic currents record
a time of dryness, i . e . , no corrosion f o r these times
of l o c a l i z e d attack.) Metals may be consumed also by
mechanisms which resemble tarnishing (Figure 5) ( 4 8 ) .
It
is proposed that reaction rates are not l i m i t e d by
d i f f u s i o n across the monolayer since i t is so t h i n ,
since i t does not prevent rapid reaction when the
adsorbed layer is thicker, and since s i m i l a r v i s c i n a l
layers do not prevent rapid reactions at electrode
surfaces in bulk e l e c t r o l y t e s .
3.4
High RH. At r e l a t i v e humidities for which
the water is more than three molecules thick (~ 65%
for many cases), water approaches the behavior of bulk
solutions. This is c e r t a i n l tru f o film
* 100
microns thick due t
cent corrosion products ( 4 , _ 5 > J ^ > ^ > 4 9 ) Corrosion in this
regime may be related to that in bulk e l e c t r o l y t e s
and s i m i l a r apparatus may be employed to study i t (44_) .
This is the threshold of c r i t i c a l RH, beyond which
substantial weight changes are reported and time of
wetness monitors indicate substantial corrosion. Below
t h i s threshold, weight loss is minor although o p t i c a l
surfaces may be degraded.
3.5 Conclusion. Although much is not known, and
quantitative data is scarce, we conclude that a model
of the adsorbed aqueous phase provides a perspective
on observations made in many d i f f e r e n t aspects of
atmospheric corrosion. The parameter which we have
used as a r a t i o n a l gauge of t h i s data in the thickness
of the water adsorbed on the oxyhydroxide surface.
This must be recognized as a crude beginning, but i t
is hoped that the model exposes questions which need
to be addressed before d e t a i l s of atmospheric corrosion
can be understood. Such work w i l l supplement the
r e l a t i v e l y large number of studies on the protection
afforded by p a r t i c u l a r s o l i d phases.
Acknowledgement s
The assistance of C. Breen, V.J. Gupta, and R.
Tremoureaux is acknowledged with thanks.

260
L i t e r a t u r e Cited
1.
EPA Publication AP-42, U.S. GPO., Wash., D.C., 1973.

R.I. Larsen J. A i r P o l l u t i o n Control Association
(1976) 26, 325.
2. R i t c h i e , I.M., "Chemisorption and Reactions on Metal
Films," ed Anderson, J.R., Academic Press, 1971.
3. Pourbaix, M., de Miranda, L.R., Cebelcor Rapp. Tech.
227 (1975).
4. Tomashov, N.D., "Theory of Corrosion and Protection
of Metals," MacMillan, N.Y. (1966).
5. Sereda, P.J., ASTM (1958), 53 ( B u l l . No. 228), (1959)
61 (No. 238), (1960) 47 (No. 246), (1968) 326 (No. 435).
6. Mansfeld, F. and Kenkel, J.V., Corros. S c i . 16, 111
(1976).
7. Huber, E.E. Jr. and K i r k C.T Jr., Surface Sci.
(1966) 5, 447.
8. Jona, F., J. Phys
9. Krueger, W.H. and Pollack, S.R., Surface S c i . (1972)
30, 263, 280.
10. Tomlinson F o r t , J r . and Wells, R.L., Surface Sci.
(1972) 32, 543.
11. I b i d . , p. 554.
12. Waclawski, B.J. and Hughey, L.R., Surface Sci.(1970)
19, 464.
13. Bowden, F.P. and T h r o s s e l l , W.R., Proc. Roy. Soc.
(1951) 209, 297.
14. Roberts, M.W. and Wood, P.R., J. Electron Spectrosc.
Relat. Phenom., (1977) 11, 431.
15. K l i e r , K., Shen, J.H. and Zettlemoyer, A.C., J. Phys.
Chem. (1973) 77, 1458.
16. K l i e r , K. and Zettlemoyer, A.C., J. C o l l o i d Interface
Sci.(1977) 58, 216.
17. Woessner, D.E. and Snowden, B.S., J. Phys. Chem.
(1963) 67, 1590.
18. I b i d . , J. Chem. Phys. (1969) 50, 1516.
19. Bass, B.D. and S t e j s k a l , E.O., J C o l l o i d Interface
Sci.(1968) 26, 271.
20. McCafferty, E., Pravdic, V. and Zettlemoyer, A.C.,
Trans. Far. Soc. (1970) 66, 1720.
21. Thorp, J.M., I b i d . , p. 1721.
22. Jonscher, A.K., Shahidi, M. and Hasted, J.B., Nature
(1975) 258, 595.
23. Sing, K.S.W., Colloques Internationaux du CNRS (1971)
201, 601.
24. Stockbridge, C.O. and Warner, A.W., "Vacuum Microbalance Technique" V o l 2, p. 71, ed R.F. Walker
Plenum Press (1962)
25. Brunauer, S., Emmett, P.H. and T e l l e r , ., J. Am.
Chem. Soc. (1938) 60, 309.

8.
PHIPPSANDR I C E
Corrosion
261
26. Brusic, V., t h i s volume.

27. Schwabe, K. and Schmidt, W., Corros. S c i . (1970) 10,
143.
28. Cohen, ., t h i s volume.
29. Foley, C.L., Kruger, J. and Bechtoldt, C.J., J.
Electrochem. Soc. (1967) 114, 994.
30. Yolken, H.T., Kruger, J. and Calvert, J.P., Corros.
S c i . (1968) 8, 103.
31. Hill, T.L.,J.Chem. Phys. (1946) 14, 268.
32. White, L., e tal,J.Am. Chem. Soc. (1949) 71, 2593.
33. Ibid., J. Am. Chem. Soc. (1952) 74, 5796.
34. Kwan, T., Freeman, M.P. and Halsey, G.D., J. Phys.
Chem. (1955) 59, 600.
35. Adamson, A.W. and Dormant, L.M., J. Am. Chem. Soc.
(1966) 88, 2055.
36. Barrer, R.M. an
(1962) 58, 2262.
37. Fripiat, J.J., e tal,J.Phys. Chem. (1965) 69, 3294.
38. Basila, M.R. and Kantner, T.R., J. Phys. Chem. (1967)
71, 467.
39. Anderson, J.H. and Parks, G.A., J. Phys. Chem. (1968)
72, 3662.
40. Kawasaki, K. and Hackerman, ., Surface Sci. (1968)
10, 299.
41. Hayward., A.T.J, and Isdale, J.D., J. Phys. D. (1969)
2, 251.
42. Lyklema, J., J. Colloid Interface Sci. (1977) 58,
242.
43. Olejnik, S., Stirling, G.C. and White, J.W., Disc
Far. Soc. (1970) 1, 187.
44. Rosenfeld, I.L., "The Atmospheric Corrosion of
Metals," NACE, Houston, TX. (1972).
45. Duncan, J.R. and Spedding, D.J., Corros. Sci. (1973)
13, 993.
46. Ibid., (1974) 14, 607.
47. Ibid., (1977) 17, 173.
48. Kroger, F.A., "The Chemistry of Imperfect Crystals,"
North Holland-American Elserier, New York (1974).
49. Takehara, Z., Saito, A. and Yoshizawa, S., Corros.
Sci. (1976) 16, 91.
R E C E I V E D September 1, 1978.

9
Corrosion Inhibition and Inhibitors
RUDOLF H. HAUSLER
Gordon Lab, Inc., 925 Patton Rd., P.O. Box 605, Great Bend, KS 67580
An Educational Lecture or Paper on Corrosion I n h i b i t i o n could e a s i l y develop into an ambitious undertaking if it were intende
ture concerned wit
i t o r s and the multitude of mechanisms proposed as explanations of t h e i r a c t i o n .
The past approaches aimed
at understanding Corrosion I n h i b i t i o n have been many,
ranging from phenomenological screening of chemical
compounds in a given environment to detailed e l e c t r o chemical adsorption studies.
Let me state that the
ultimate purpose of i n h i b i t o r studies ought to be the
development of p r e d i c t i v e criteria for i n h i b i t o r e f f e c tiveness rather than the mere explanation of e x p e r i mental Results or speculation about possible mechanisms.
While such p r e d i c t i v e criteria have been developed in a few cases it appears that most mechanistic
studies have merely contributed to speculative guide
l i n e s h e l p f u l in the unraveling process of i n h i b i t o r
a c t i o n , but have been far from successful in providing
a complete understanding of p r a c t i c a l i n h i b i t i o n phenomena l e t alone p r e d i c t i v e criteria for more e f f e c t i v e
molecules.
The reason for t h i s state of a f f a i r s may be seen
in past emphasis on surface phenomenological studies
which attempted to model the metal surface as an array
of surface atoms with some valences saturated by subsurface metal atoms and other valences saturated by
ions or molecules making up the environment.
This
model led to the d e s c r i p t i o n of the interface in terms
of the Helmholz and Guy-Chapman double layer t h e o r i e s ,
and i n h i b i t o r s were v i s u a l i z e d as i n t e r f e r i n g with the
double layer structure through adsorption on the surface atoms of the metal, thereby a l t e r i n g the e l e c t r o chemical reaction rates which are governed by the energetics of the double l a y e r . While t h i s model has been
0-8412-0471-3/79/47-089-262$13.85/0

9.
HAUSLER
Corrosion
Inhibition
263
q u i t e s u c c e s s f u l in e x p l a i n i n g changes o f e l e c t r o c h e m i c a l r e a c t i o n r a t e s as a consequence o f changes o c c u r r i n g in the c o m p o s i t i o n o f the e l e c t r o l y t e i t has not

been s u c c e s s f u l in d e s c r i b i n g t y p i c a l p r a c t i c a l i n h i b i t i o n phenomena.
A r a t h e r l a r g e body o f e v i d e n c e has been accumul a t e d o v e r the p a s t 10 t o 15 y e a r s i n d i c a t i n g t h a t the
c h e m i s t r y o f the i n t e r p h a s e between the m e t a l per se
and the homogeneous b u l k o f the e l e c t r o l y t e may
determine the k i n e t i c s o f t h e c o r r o s i o n p r o c e s s .
This i n t e r phase must be v i s u a l i z e d as b e i n g d i s t i n c t l y d i f f e r e n t
in c o m p o s i t i o n from e i t h e r the m e t a l or the e l e c t r o l y t e
and e x t e n d i n g from m i c r o s c o p i c t o perhaps even macroscopic dimensions.
As a consequence the o v e r a l l k i n e t i c s o f the c o r r o s i o n p r o c e s s are d e t e r m i n e d by a comp l e x i n t e r p l a y between the r e a c t i o n r a t e s at the two
i n t e r f a c e s made up b
phase and t r a n s p o r t
I f the c o r r o s i o n p r o c e s s is modeled in t h i s manner,
then the c o r r o s i o n i n h i b i t i o n phenomena must be seen
as :
a) the i n t e r a c t i o n o f a c h e m i c a l substance
w i t h the o u t e r s u r f a c e o f the i n t e r p h a s e ;
b) an i n t e r a c t i o n w i t h the i n t e r p h a s e i t s e l f
t h e r e b y changing i t s c h e m i c a l n a t u r e ;
c) or the f o r m a t i o n o f a new
interphase.
The f o l l o w i n g d i s c u s s i o n w i l l t h e r e f o r e make but
a weak attempt t o r e v i e w p a s t approaches t o i n h i b i t i o n
theory.
R a t h e r , emphasis w i l l be p l a c e d on the i n t e r phase c o n c e p t .
I t is hoped t h a t t h e r e a d e r w i l l t h u s
be o f f e r e d a s h o r t i n t r o d u c t i o n t o c o r r o s i o n i n h i b i t i o n
as w e l l as b e i n g s t i m u l a t e d t o f u r t h e r i n v e s t i g a t i v e
e f f o r t s in t h e f i e l d o f c o r r o s i o n i n h i b i t i o n .
The
Corrosion
Mechanism
C o r r o s i o n i n h i b i t i o n is g e n e r a l l y d e s c r i b e d as the
i n t e r f e r e n c e o f a substance f o r e i g n t o the c o r r o s i v e
medium w i t h the c o r r o s i o n r e a c t i o n o r r e a c t i o n s , and i t
is v i s u a l i z e d t h a t such i n t e r f e r e n c e t a k e s p l a c e
t h r o u g h the a d s o r p t i o n o f the i n h i b i t o r on the m e t a l
surface.
While t h i s concept has been s u c c e s s f u l in
many i d e a l i z e d s i t u a t i o n s , such as the c o r r o s i o n o f
i r o n in h y d r o c h l o r i c a c i d CD i t s a p p l i c a t i o n has been
f a r t o o g e n e r a l and too p r o l i f i c in o r d e r t o advance
the u n d e r s t a n d i n g o f c o r r o s i o n i n h i b i t i o n in any s i g n ificant
way.
I t may t h e r e f o r e be h e l p f u l t o d i s c u s s b r i e f l y a
k i n e t i c model o f the c o r r o s i o n p r o c e s s i t s e l f and t h e n
d e r i v e from i t t h e v a r i o u s ways in which i n h i b i t i o n can

264
take place.
T h i s appears a l l the more n e c e s s a r y as c o r r o s i o n a f t e r more t h a n 5 0 y e a r s o f i n t e n s i v e r e s e a r c h
is s t i l l c o n s i d e r e d in many t e x t b o o k s t o be a p u r e l y
chemical process, while only s p e c i a l l i m i t i n g cases
such as g a l v a n i c c o r r o s i o n and perhaps p i t t i n g are r e c o g n i z e d as e l e c t r o c h e m i c a l in n a t u r e .
Let us emphasize from the b e g i n n i n g t h a t a l l c o r r o s i o n (the o x i d a t i v e c o n v e r s i o n o f a m e t a l t o i t s meta l i o n s ) is e l e c t r o c h e m i c a l in n a t u r e .
This implies
the e x i s t e n c e o f s i m u l t a n e o u s a n o d i c and c a t h o d i c c u r r e n t s o f e q u a l magnitude a c r o s s the i n t e r f a c e o f the
metal.
I t is by no means n e c e s s a r y
( a l t h o u g h somet i m e s u s e f u l ) , t o p o s t u l a t e permanent l o c a l i z e d anodes
and cathodes as a m i c r o s c o p i c concept w i t h f i x e d space
c o o r d i n a t e s in o r d e r t o d e v e l o p a k i n e t i c model a p p l i c a b l e t o the r a t e s o f the c o r r o s i o n p r o c e s s e s .
The c o r rosion reactions, tha
m e t a l and t h e c a t h o d i
may indeed t a k e p l a c e w i t h s t a t i s t i c a l d i s t r i b u t i o n in
time and space on the s u r f a c e o f the m e t a l .
The p r o o f
o f t h i s t h e s i s was g i v e n by Wagner and Traud (JL) in
1938 by means o f t h e d i s c u s s i o n o f the l i m i t i n g case
o f z i n c amalgam d i s s o l u t i o n . L i q u i d z i n c amalgam must
be c o n s i d e r e d a c o m p l e t e l y homogeneous phase where i t
is i m p o s s i b l e t o d e f i n e , in a r i g o r o u s thermodynamic
sense, l o c a l g a l v a n i c elements on the s u r f a c e .
The
d i s s o l u t i o n o f z i n c amalgam in d i l u t e h y d r o c h l o r i c a c i d
c o u l d t h e r e f o r e proceed by a c h e m i c a l mechanism as
shown in e q u a t i o n s 1 and 2:
Zn + 2H+
{Zn H21
**{zn H }
2 +
(1)
Zn
+ 2
+ H
(2)
T h i s model v i s u a l i z e s t h a t z i n c atoms on the s u r f a c e o f the amalgam form a t r a n s i t i o n complex w i t h two

p r o t o n s which s u b s e q u e n t l y d i s s o c i a t e s i n t o z i n c i o n s
and hydrogen.
I f t h i s mechanism were t o p r e v a i l , t h e
r a t e o f hydrogen e v o l u t i o n ( o r o x i d a t i o n o f z i n c ) would
have t o depend on the c o n c e n t r a t i o n o f t h e t r a n s i t i o n
complex i f t h e second r e a c t i o n were r a t e d e t e r m i n i n g ,
or on the p r o d u c t o f the c o n c e n t r a t i o n s o f z i n c and the
p r o t o n s i f the f i r s t r e a c t i o n were r a t e d e t e r m i n i n g .
Wagner and Traud, however, have shown t h a t the r a t e o f
the hydrogen e v o l u t i o n on a mercury s u r f a c e is i n d e pendent o f s m a l l c o n c e n t r a t i o n s o f z i n c and can t h e r e f o r e be determined e l e c t r o c h e m i c a l l y on a pure mercury
electrode.
Conversely, the o x i d a t i o n o f z i n c from z i n c
amalgam is e s s e n t i a l l y independent o f the pH and can be
measured at h i g h pH w i t h o u t i n t e r f e r i n g hydrogen e v o lution.
One can t h e r e f o r e determine t h e s e two r a t e s

9.
HAUSLER
Corrosion
Inhibition
265
over a wide p o t e n t i a l range and in the case o f the hydrogen e v o l u t i o n f o r d i f f e r e n t p H s .

S i n c e in the
" c o r r o s i o n " o f z i n c amalgam the o x i d a t i o n o f the z i n c
and the e v o l u t i o n o f hydrogen have t o p r o c e e d at the
same r a t e in o r d e r t o p r e s e r v e the laws o f e l e c t r o n e u t r a l i t y in the system, one can now use the a b o v e . d e t e r mined r a t e c h a r a c t e r i s t i c s f o r the two r e a c t i o n s in o r der t o p r e d i c t the r e s t p o t e n t i a l o f c o r r o d i n g z i n c amalgam, and t o determine i t s c o r r o s i o n r a t e .
The r e s u l t can t h e n be v e r i f i e d i n d e p e n d e n t l y by d e t e r m i n i n g the
r a t e o f hydrogen e v o l u t i o n from z i n c amalgam v o l u m e t r i c a l l y and by a l s o a n a l y z i n g f o r z i n c in the r e s u l t i n g
solution.
These experiments have i n d e e d been s u c c e s s f u l and are c o n s i d e r e d s u f f i c i e n t p r o o f f o r the p o s t u l a t e o f the e l e c t r o c h e m i c a l mechanism f o r the d i s s o l u t i o n o f z i n c amalgam in d i l u t e h y d r o c h l o r i c a c i d , as
shown by e q u a t i o n s 3
o d i c r e a c t i o n s procee
each o t h e r .
For a more d e t a i l e d d i s c u s s i o n o f the d i s
s o l u t i o n o f z i n c amalgam the r e a d e r is r e f e r r e d t o the
o r i g i n a l l i t e r a t u r e o r a d i s c u s s i o n by H. Kaesche ( 3 ) .
f
Zn
* Zn
+
2H *H
+ 2
+ 2e
- 2e
(3)
(4)
f h i s v e r i f i c a t i o n o f the e l e c t r o c h e m i c a l n a t u r e o f the
c o r r o s i o n p r o c e s s a l s o l e a d s t o the r e a l i z a t i o n o f f o u r
d i s t i n c t and s e p a r a t e b a s i c p r o c e s s e s i n v o l v e d in
c o r r o s i o n , which are l i n k e d t o g e t h e r m e r e l y by the
n e c e s s i t y o f p r e s e r v i n g e l e c t r o n e u t r a l i t y in the o v e r a l l reaction.
These are
a) the a n o d i c or o x i d a t i v e p r o c e s s ;
b) the c a t h o d i c o r r e d u c t i v e p r o c e s s ;
c) the e l e c t r o n i c charge t r a n s f e r p r o c e s s in b o t h
d i r e c t i o n s a c r o s s the i n t e r f a c e ;
d) the i o n i c charge t r a n s f e r p r o c e s s which is r e q u i r e d t o m a i n t a i n e l e c t r o n e u t r a l i t y on the
e l e c t r o l y t e s i d e due t o the d i s a p p e a r a n c e o f
i o n i c charges in the c a t h o d i c p r o c e s s and the
f o r m a t i o n o f i o n i c charges in the a n o d i c p r o cess .
One o f t h e s e f o u r r e a c t i o n s is u s u a l l y the s l o w e s t , and
r a t e d e t e r m i n i n g f o r the o v e r a l l p r o c e s s .
Corrosion
i n h i b i t i o n t a k e s advantage o f t h i s c o m p l e x i t y o f r e a c t i o n s by a t t e m p t i n g t o i n t e r f e r e w i t h any o f them
i n d i v i d u a l l y or j o i n t l y .
Thus a c o r r o s i o n i n h i b i t o r
may f u r t h e r slow the r a t e o f the s l o w e s t r e a c t i o n or
may b r i n g about a r a t e l i m i t a t i o n o f one or the o t h e r
o f the r e m a i n i n g t h r e e p r o c e s s e s .
While i t is g e n e r a l l y known t h a t c o r r o s i o n i n h i b i t o r s may a f f e c t the an-

266
o d i c o r the c a t h o d i c r e a c t i o n , i t is l e s s w e l l known
t h a t i n h i b i t i v e means may a f f e c t e i t h e r the e l e c t r o l y t i c c o n d u c t i o n or even the e l e c t r o n i c c o n d u c t i o n p r o cess .
Systematic C l a s s i f i c a t i o n
Of C o r r o s i o n
Inhibitors
The s e v e r a l thousand s u b s t a n c e s which have in the

p a s t been o b s e r v e d t o have c o r r o s i o n i n h i b i t i v e p r o p e r t i e s have o f t e n been c l a s s i f i e d in v a r i o u s ways.
The s t a r t i n g p o i n t f o r such c l a s s i f i c a t i o n is the p o i n t
o f i n t e r f e r e n c e w i t h the above s k e t c h e d c o r r o s i o n mechanism e i t h e r in a p h e n o m e n o l o g i c a l or in a m e c h a n i s t i c
way.
A simple system f o r c l a s s i f i c a t i o n , which w i l l
be d i s c u s s e d in more d e t a i l l a t e r , is based on whether
the i n h i b i t o r i n t e r f e r e s w i t h the a n o d i c o r c a t h o d i c
reaction.
Thus i n h i b i t o r
cathodic i n h i b i t o r s
shown t o be too s i m p l i s t i c and a more complex c l a s s i f i c a t i o n was worked out by H. F i s c h e r (JjJ on the b a s i s o f
where, i n s t e a d o f how, in the complex i n t e r p h a s e o f a
m e t a l - e l e c t r o l y t e system the i n h i b i t o r i n t e r f e r e s w i t h
the c o r r o s i o n r e a c t i o n s .
The m e t a l - e l e c t r o l y t e i n t e r phase can be v i s u a l i z e d as c o n s i s t i n g o f (a) the i n t e r f a c e per se, and (b) an e l e c t r o l y t e l a y e r i n t e r p o s e d
between the i n t e r f a c e and the b u l k o f the e l e c t r o l y t e .
On t h i s b a s i s F i s h e r d i s t i n g u i s h e d as shown in T a b l e 1,
between " I n t e r f a c e I n h i b i t i o n " and " E l e c t r o l y t e L a y e r
Inhibition."
I n t e r f a c e I n h i b i t i o n comes about by s u b s t a n c e s
which p o s i t i o n themselves immediately at the s u r f a c e
o f the m e t a l and d e c r e a s e the r a t e s o f p h y s i c a l , chemi c a l o r e l e c t r o c h e m i c a l p r o c e s s e s in the c o r r o s i o n
mechanism.
Such p r o c e s s e s may
be:
a) the charge t r a n s f e r per se;
b) the i n t e r r u p t i o n o f the c r y s t a l l a t t i c e ;
c) the p a r t i a l s t e p s i n v o l v e d in the a n o d i c o r
c a t h o d i c r e a c t i o n s , t h a t is c h e m i c a l r e a c t i o n s
e i t h e r p r e c e d i n g or f o l l o w i n g the charge t r a n s fer reactions.
D i s c u s s i n g i n t e r f a c e i n h i b i t i o n one f i n d s t h a t
the pure s q u e e z i n g out e f f e c t ( s a l t i n g out e f f e c t ) ,
which may c o n c e n t r a t e i n h i b i t i n g n e u t r a l m o l e c u l e s at
the m e t a l e l e c t r o l y t e i n t e r f a c e , w i l l be r a t h e r r a r e .
However, i t is p o s s i b l e t h a t the a c t i v i t y o f i o n s or
m o l e c u l e s t a k i n g p l a c e in the c o r r o s i o n r e a c t i o n is dec r e a s e d simply by the a c c u m u l a t i o n o f n e u t r a l m o l e c u l e s
in the v i c i n i t y o f the m e t a l s u r f a c e .
Such s u b s t a n c e s
c o u l d be a l c o h o l , water s o l u b l e i n e r t s o l i d s in gene r a l , or i n e r t i o n s .

9.
HAUSLER
Corrosion
267
Inhibition
Table I
(A)
Causes o f I n t e r f a c e - I n h i b i t i o n and
I n h i b i t ion
Electrolyte-Layer-
1.
Interface-Inhibition.
1.1 caused by the
s q u e e z i n g out
effect.
1.2 caused by a d s o r p t i o n .
1.3 caused by e l e c t r o s o r p t i o n .
1.4 caused by coverage w i t h a p o l y m o l e c u l a r o r
polymerous l a y e r .
2.
Electrolyte-Layer-Inhibition.
2.1 m e c h a n i c a l E. caused by
2.11 c o l l o i d s o r s u s p e n s i o n s
2.12 v i s c o u
2.13 pores in
ers .
2.2 c h e m i c a l E. caused by s u b s t a n c e s r e a c t i n g w i t h
components o f homogeneous p a r t i a l r e a c t i o n s o f
the e l e c t r o d e r e a c t i o n .
2.3 e l e c t r o c h e m i c a l E. caused by changes o f t h e
p o t e n t i a l in the d i f f u s e double l a y e r dependent
on a coverage o f the i n t e r f a c e w i t h i o n s
M o s t l y however, t h e s e and o t h e r m o l e c u l e s as w e l l
as i o n s or i o n p a i r s coming from the e l e c t r o l y t e may
be adsorbed on the m e t a l l i c ( o r s e m i c o n d u c t i v e ) p a r t
o f the i n t e r f a c e .
D i s r e g a r d i n g the s p e c i a l case o f the
p o t e n t i a l o f z e r o charge at the m e t a l l i c s u r f a c e , the
conductor w i l l u s u a l l y c a r r y a p o s i t i v e or negative
charge which may f a v o r i t s coverage w i t h charged o r
p o l a r s u b s t a n c e s o c c u r i n g near t h e i n t e r f a c e .
I t is
v e r y d i f f i c u l t , however, t o d i s t i n g u i s h between pure
a d s o r p t i o n o f n e u t r a l m o l e c u l e s on the s u r f a c e o f t h e
c o r r o d i n g m e t a l by means o f Van d e r Waals or a chemi c a l f o r c e s , and e l e c t r o s o r p t i o n which t a k e s p l a c e by
p o t e n t i a l dependent e l e c t r o s t a t i c f o r c e s .
O f t e n the
two mechanims o p e r a t e in c o n j u n c t i o n . I t has been
shown f o r i n s t a n c e , t h a t o r g a n i c amines become much
more e f f e c t i v e c o r r o s i o n i n h i b i t o r s in a c i d medium i f
a h a l i d e is p r e s e n t . H a l i d e i o n s , p a r t i c u l a r l y i o d i d e ,
a r e s t r o n g l y adsorbed on m e t a l s u r f a c e s thus f o r m i n g a
n e g a t i v e l y charged l a y e r on the m e t a l s u r f a c e onto
which p r o t o n a t e d o r g a n i c amines adsorb s u b s e q u e n t l y ,
with a r e s u l t i n g i n h i b i t i o n of corrosion reactions.
F i n a l l y , one can t a l k about an i n t e r f a c e e f f e c t
which is caused by coverage o f the m e t a l s u r f a c e w i t h
a polymerous l a y e r .
Some a u t h o r s t h i n k t h a t c e r t a i n

268
i n h i b i t o r s such as the a c e t y l e n i c ones form a polymer

l a y e r on the s u r f a c e o f the m e t a l .
In o t h e r words, the
monomeric i n h i b i t o r m o l e c u l e s undergo e i t h e r c h e m i c a l
or e l e c t r o c h e m i c a l r e a c t i o n on the m e t a l s u r f a c e such
t h a t a p o l y m e r i c two d i m e n s i o n a l system is formed which
t i g h t l y adheres t o the m e t a l s u r f a c e and i n t e r f e r e s
w i t h the r a t e s o f the c o r r o s i o n r e a c t i o n s .
A l l o f the above i n h i b i t i o n phenomena are v i s u a l i z e d as t a k i n g p l a c e immediately on the m e t a l s u r f a c e
o f the c o r r o d i n g specimen. A p p a r e n t l y , t h e r e are ways
t h a t one can a f f e c t c o r r o s i o n r e a c t i o n s by i n t e r f e r i n g
w i t h p r o c e s s e s which are not on t h e s u r f a c e , but t h o s e
in the v i c i n i t y of the s u r f a c e , namely in the e l e c t r o l y t e l a y e r c l o s e s t t o the s u r f a c e .
Electrolyte layer
i n h i b i t i o n may h i n d e r the f o l l o w i n g p a r t i a l s t e p s o f
electrode reactions:
1) T r a n s p o r t o
t i o n s t o o r fro
2 ) P a r t i a l steps o f the homogeneous c h e m i c a l r e a c t i o n s w i t h i n the e l e c t r o l y t e l a y e r .
This
can be a c c o m p l i s h e d by:
a) p u r e l y m e c h a n i c a l o b s t a c l e s assembled in the
e l e c t r o l y t e l a y e r (mechanical e l e c t r o l y t e
layer i n h i b i t i o n ) ;
b) by c h e m i c a l r e a c t i o n s o f components o f the
e l e c t r o d e r e a c t i o n s w i t h s u b s t a n c e s assemb l e d in the e l e c t r o l y t e l a y e r ( c h e m i c a l
electrolyte layer inhibition);
c) by e l e c t r o c h e m i c a l e f f e c t s such as a change
o f the z e t a p c t e n t i a l in the d i f f u s e p a r t o f
the double l a y e r which c o n t r o l s the m i g r a t i o n o f components o f e l e c t r o d e r e a c t i o n s .
T h i s is c a l l e d the e l e c t r o c h e m i c a l e l e c t r o lyte layer inhibition.
For more d e t a i l e d d i s c u s s i o n o f the v a r i o u s phen o m e n o l o g i c a l i n h b i t i o n mechanism the r e a d e r is r e f e r r e d
t o the o r i g i n a l l i t e r a t u r e . (4_)
I t is o b v i o u s now t h a t c o r r o s i o n i n h i b i t i o n is not
a simple phenomena, and a d e c i s i o n may have t o be made
whether i t may be more u s e f u l t o d i s c u s s c o r r o s i o n inh i b i t i o n a l o n g m e c h a n i s t i c l i n e s or by means o f a t a b u l a t i o n o f c h e m i c a l compounds which have been found e f f e c t i v e under s p e c i f i c c i r c u m s t a n c e s .
However, the d i g e s t i o n o f e x h a u s t i v e t a b l e s o f c h e m i c a l compounds and
t h e i r a p p l i c a t i o n as c o r r o s i o n i n h i b i t o r s as p r e s e n t e d
in C. Nathan's book (JL) l e a v e s the r e a d e r as d i s s a t i s f i e d and p u z z l e d as do e l a b o r a t e c l a s s i f i c a t i o n s y s tems o f c o r r o s i o n i n h i b i t o r s which i n v a r i a b l y l a c k exp e r i m e n t a l s u b s t a n t i a t i o n and have at t h i s stage l i t t l e
p r e d i c t i v e value.

9.
Corrosion
HAUSLER
269
Inhibition
As a consequence i t is judged t o be more u s e f u l

f o r t h e n o v i c e in t h e f i e l d o f c o r r o s i o n i n h i b i t i o n t o
f a m i l i a r i z e h i m s e l f w i t h some o f t h e fundamental in
v e s t i g a t i v e means and s u b s e q u e n t l y be c o n f r o n t e d w i t h
some s p e c i a l cases o f c o r r o s i o n i n h i b i t i o n which may o r
may not l e n d themselves t o g e n e r a l i z a t i o n .
Experimental Observation of Corrosion I n h i b i t i o n
The study o f c o r r o s i o n p r o c e s s e s in r e c e n t y e a r s
has been almost e n t i r e l y based on t h e so c a l l e d Evans
diagram.
C o n s i d e r i n g how o f t e n t h i s diagram has been
misused o r m i s r e p r e s e n t e d suggests t h a t a b r i e f d i s
c u s s i o n may a g a i n be in o r d e r at t h e r i s k o f b e i n g
r e p e t i v e or t r i v i a l .
The Evans diagram ( 1 ) is a g r a p h i c a l p r e s e n t a t i o n
in s e m i l o g a r i t h m i c c o o r d i n a t e
ic
reaction rate
pendent on p o t e n t i a l .
The b a s i s f o r t h e Evans diagram
is t h e c o r r o s i o n model d i s c u s s e d above:
Me
^Me
n +
+ ne
(5)
Ox + n e ^ R e d -
(6)
These p a r t i a l r e a c t i o n s proceed w i t h e q u a l r e a c
t i o n r a t e s when t h e m e t a l is f r e e l y c o r r o d i n g . I n o r
der t o e x p r e s s t h e r e a c t i o n r a t e s in terms o f a c u r
r e n t , t h e c o n v e r s i o n p e r time is m u l t i p l i e d by t h e
Faraday c o n s t a n t a c c o r d i n g t o t h e f o l l o w i n g e q u a t i o n :
J
(7)
= Q' F
Where J e q u a l s c u r r e n t , number o f e l e c t r o n s t r a n s
f e r r e d p e r molecule, F e q u a l s Faraday c o n s t a n t and Q" is
the r a t e o f t h e r e a c t i o n e x p r e s s e d in terms o f moles
per u n i t t i m e .
I f t h e above e q u a t i o n is d i v i d e d by t h e
s u r f a c e a r e a t h e c u r r e n t d e n s i t y can be e x p r e s s e d as
follows :
J
- _ .
F.n
(8)
The p a r t i a l a n o d i c ( i ) and c a t h o d i c ( i ) c u r r e n t
d e n s i t i e s a r e then e x p r e s s e d as e x p o n e n t i a l f u n c t i o n s
of the o v e r - p o t e n t i a l ( n
n ) which is t h e d i f f e r e n c e
between t h e o p e r a t i n g p o t e n t i a l () and t h e e q u i l i b r i u m
p o t e n t i a l ( E E ) of the p a r t i c u l a r p a r t i a l r e a c t i o n .
These r e l a t i o n s h i p s a r e shown g r a p h i c a l l y and e x p l i c i t
l y in F i g . 1 . Thus by d e f i n i n g t h e a n o d i c and c a t h o d i c
c u r r e n t p o t e n t i a l r e l a t i o n s h i p s f o r a c o r r o d i n g system
a

270
and by p l o t t i n g them as shown in a p o t e n t i a l vs l o g i

diagram, one q u i c k l y f i n d s the p o i n t where the two
l i n e s i n t e r c e p t , which is the p o t e n t i a l at which a n o d i c
and c a t h o d i c r e a c t i o n r a t e s are e q u a l .
The c u r r e n t at
t h i s p o i n t becomes c o r r o s i o n c u r r e n t o r c o r r o s i o n r a t e
w h i l e the c o r r e s p o n d i n g p o t e n t i a l is the c o r r o s i o n potential .
I t must be r e a l i z e d t h a t in a c o r r o d i n g system the
p a r t i a l c u r r e n t s cannot be d i r e c t l y o b s e r v e d .
If a
c o r r o d i n g p i e c e o f m e t a l is made an e l e c t r o d e in an
e l e c t r o c h e m i c a l c e l l the c o r r o s i o n r e a c t i o n s a l r e a d y p r o ceed w i t h a g i v e n r a t e .
The m e t a l w i l l t h e r e f o r e a s sume t h e c o r r o s i o n p o t e n t i a l ( e c o r r ) and the system is
in a s t e a d y s t a t e c o n d i t i o n as opposed t o an e q u i l i brium s t a t e .
No c u r r e n t w i l l f l o w in the e x t e r n a l c i r c u i t at t h i s p o i n t .
I f now by means o f an e x t e r n a l
c i r c u i t the p o t e n t i a
in the a n o d i c o r c a t h o d i
o d i c c u r r e n t w i l l f l o w in the e x t e r n a l c i r c u i t ( H ^ i e x t ) .
T h i s o b s e r v e d e x t e r n a l c u r r e n t is the e q u i v a l e n t o f t h e
a l g e b r a i c sum o f the a n o d i c and c a t h o d i c p a r t i a l c u r r e n t s and can t h e r e f o r e be p r e d i c t e d from the i n d i v i d u a l c h a r a c t e r i s t i c s as shown in F i g . l .
I f the o p e r a t i n g p o t e n t i a l is s u f f i c i e n t l y n e g a t i v e o f the c o r r o s i o n p o t e n t i a l , the c u r r e n t - p o t e n t i a l b e h a v i o r o f the
e x t e r n a l c u r r e n t w i l l resemble the p a r t i a l c a t h o d i c
c h a r a c t e r i s t i c because under t h e s e c o n d i t i o n s the ano d i c c u r r e n t has become e x t r e m e l y s m a l l . The p o t e n t i a l
r e g i o n s where e i t h e r o f t h e p a r t i a l r e a c t i o n s is negl i g i b l y s m a l l w i t h r e s p e c t t o the o t h e r are c a l l e d the
T a f e l r e g i o n s . The c u r r e n t p o t e n t i a l b e h a v i o r in the
T a f e l r e g i o n s o f an a c t i v e l y c o r r o s i n g p i e c e o f m e t a l
are o f t e n used t o draw c o n c l u s i o n s w i t h r e s p e c t t o the
mechanism o f t h e p a r t i a l c o r r o s i o n r e a c t i o n s .
I t is
t h e r e f o r e in p r i n c i p a l p o s s i b l e t o e s t a b l i s h the Evans
diagram from fundamental knowledge o f the i n d i v i d u a l
r e a c t i o n s o r e x p e r i m e n t a l l y by s t u d y i n g the p o l a r i z a t i o n b e h a v i o r o f a c o r r o d i n g p i e c e o f m e t a l in a g i v e n
environment.
F o r more d e t a i l e d d e r i v a t i o n o f e l e c t r o c h e m i c a l r a t e e q u a t i o n s see
CD.
I t is i m p o r t a n t t o remember t h a t some assumptions
have been made in the d e r i v a t i o n o f F i g . l .
F i r s t , the
e q u a t i o n s g i v e n t h e r e a r e a p p l i c a b l e o n l y i f the e l e c t r o n t r a n s f e r is the r a t e d e t e r m i n i n g step in the part i a l c o r r o s i o n r e a c t i o n s . T h i s is i m p o r t a n t w i t h r e s p e c t t o t h e c a l c u l a t i o n o f the T a f e l s l o p e (RT/anF) o r
the i n t e r p r e t a t i o n o f an e x p e r i m e n t a l one.
I t is f u r t h e r assumed t h a t d u r i n g the p o l a r i z a t i o n o f the t e s t
e l e c t r o d e ( c o r r o d i n g p i e c e o f m e t a l ) the c o m p o s i t i o n
of
the s o l u t i o n in t h e v i c i n i t y o f the e l e c t r o d e remains

9.
HAUSLER
Corrosion
271
Inhibition
constant.
T h i s is o f t e n not the case s i n c e the consumption o f an o x i d a n t (oxygen o r p r o t o n s ) d u r i n g c a t h odic p o l a r i z a t i o n r a p i d l y leads to d i f f u s i o n l i m i t a t i o n
( d i f f u s i o n o v e r - p o t e n t i a l ) w h i l e secondary r e a c t i o n s
d u r i n g p o l a r i z a t i o n in the a n o d i c d i r e c t i o n o f t e n l e a d
t o p r e c i p i t a t i o n o f m e t a l h y d r o x i d e s and c o n s e q u e n t l y
p a s s i v a t i o n phenomena.
In s p i t e o f such e x p e r i m e n t a l d i f f i c u l t i e s the
Evans diagram has been e x t r e m e l y u s e f u l in d e t e r m i n ing c e r t a i n c h a r a c t e r i s t i c s of i n h i b i t o r s .
In a c i d sol u t i o n s f o r example, the e l e c t r o d e r e a c t i o n s f o l l o w a
b e h a v i o r which is q u i t e p r e d i c t a b l e on the b a s i s o f the
e l e c t r o n t r a n s f e r b e i n g the r a t e d e t e r m i n i n g s t e p .
Thus Hackerman (JJ and Nobe (JL) have s t u d i e d such s y s tems e x t e n s i v e l y and found t h a t the e f f e c t i v e n e s s o f
c e r t a i n amine i n h i b i t o r s can be e x p l a i n e d by t h e i r adsorption behavior.
Th
proved t o be p r e d i c t a b l
s t r u c t u r e and c o n f i g u r a t i o n .
In n e u t r a l or a l k a l i n e s o l u t i o n , or s o l u t i o n s o f
low c o n d u c t i v i t y , however, one f i n d s v e r y s m a l l T a f a e l
r e g i o n s , or the T a f a e l r e g i o n s are e s s e n t i a l l y n o n e x i s tent.
The r e a s o n s f o r such b e h a v i o r are many:
a) S t e r n (JL) f o r example has shown t h a t the c a t h o d i c p o l a r i z a t i o n c u r v e s f o r i r o n c o r r o d i n g in oxygen
f r e e sodium c h l o r i d e s o l u t i o n show hydrogen i o n d i f f u s i o n l i m i t a t i o n at a c u r r e n t o f 1 0 "
a/cm at a pH o f
2.
Thus in such systems above a pH 1.5 e s s e n t i a l l y no
T a f e l r e g i o n is o b s e r v e d due t o a d i f f u s i o n o v e r - p o tential.
b) R e s i s t a n c e s or o v e r - p o t e n t i a l s o t h e r than t h o s e
d e t e r m i n i n g the r a t e o f the e l e c t r o n t r a n s f e r r e a c t i o n
are o f t e n i n c l u d e d in the c u r r e n t p o t e n t i a l measurement. The most f r e q u e n t s i t u a t i o n is the i n c l u s i o n
o f an ohmic r e s i s t a n c e which o c c u r s between the worki n g e l e c t r o d e and the r e f e r e n c e e l e c t r o d e .
Such ohmic
e l e c t r o l y t e r e s i s t a n c e s can e a s i l y be determined by
p o s i t i o n i n g the r e f e r e n c e e l e c t r o d e at v a r y i n g d i s t a n c e s
from
the
working e l e c t r o d e , or by v a r i o u s mathematic a l p r o c e d u r e s i n c l u d i n g a u t o m a t i c i R - d r o p compensating
electronic devices.
M a n s f e l d has r e c e n t l y d i s c u s s e d
the e f f e c t o f such r e s i s t a n c e on c u r r e n t p o t e n t i a l
c u r v e s (10).
A more s e r i o u s r e s i s t a n c e o f t e n i n f l u e n c i n g the p o t e n t i a l d e t e r m i n a t i o n in p o l a r i z a t i o n s t u d i e s
is caused by the f o r m a t i o n o f . a c o r r o s i o n p r o d u c t l a y e r
on the s u r f a c e o f the c o r r o d i n g t e s t e l e c t r o d e .
This
s i t u a t i o n is c o n s i d e r a b l y more complex because, f i r s t ,
t h i s a d d i t i o n a l r e s i s t a n c e is most l i k e l y not ohmic in
n a t u r e due t o the s e m i c o n d u c t i n g p r o p e r t i e s o f the c o r r o s i o n p r o d u c t l a y e r and second, a n o d i c and c a t h o d i c
4

272
CORROSION
CHEMISTRY
r e a c t i o n s do not n e c e s s a r i l y t a k e p l a c e at the same l o cation.

Thus the a n o d i c r e a c t i o n can be v i s u a l i z e d as
t a k i n g p l a c e at the m e t a l - s c a l e i n t e r f a c e w h i l e t h e
c a t h o d i c r e a c t i o n may t a k e p l a c e at t h e s c a l e - e l e c t r o l y t e i n t e r f a c e . The r e s u l t a n t p o l a r i z a t i o n diagram is
shown in F i g . 2 .
Note t h a t not o n l y the e x t e r n a l
c u r r e n t is s u b j e c t t o an iR drop (the case most o f t e n
d i s c u s s e d ) but the p a r t i a l c u r r e n t s are a l s o s u b j e c t t o
a d i s t o r t i o n caused by t h e a d d i t i o n a l r e s i s t a n c e .
It
must f u r t h e r be remembered t h a t the r e s i t a n c e may
be
d i f f e r e n t in magnitude f o r the c a t h o d i c and a n o d i c p a r t i a l currents.
T h i s s i t u a t i o n was d i s c u s s e d by H a u s l e r
( 1 1 ) in some d e t a i l .
Effect
Of
I n h i b i t o r s On
P o l a r i z a t i o n Behavior
One o f the mos

f i c u l t to understan
is in f a c t t h a t i n h i b i t o r s do not a f f e c t a n o d i c and
c a t h o d i c r e a c t i o n s t o the same degree.
Thus one f i n d s ,
as shown in F i g . 3
t h a t in some i n s t a n c e s the c a t h o d i c r e a c t i o n r a t e is r e d u c e d w h i l e t h e a n o d i c r e a c t i o n
r a t e remains the same or v i c e v e r s a .
As can r e a d i l y be
u n d e r s t o o d from t h e diagram in F i g . 3 , t h i s d i s t i n c t i o n can be made on the b a s i s o f a s h i f t in the c o r r o s i o n p o t e n t i a l and i f more d e t a i l e d i n f o r m a t i o n is r e q u i r e d from a complete study o f the p o l a r i z a t i o n
curves.
A b r i e f remark maybe in o r d e r here w i t h r e s p e c t t o the t e r m i n o l o g y used in such c a s e s , as i t is
o f t e n c o n f u s i n g : C a t h o d i c i n h i b i t i o n r e s u l t s in a s h i f t
o f t h e c o r r o s i o n p o t e n t i a l in the a n o d i c or n e g a t i v e
d i r e c t i o n w h i l e a n o d i c i n h i b i t i o n r e s u l t s in a p o t e n t i a l s h i f t in the c a t h o d i c or more p o s i t i v e d i r e c t i o n .
I t has been shown in t h e l i t e r a t u r e many t i m e s t h a t
some systems a r e c l a s s i c a l l y behaved as w i l l be d i s c u s s e d in more d e t a i l e d below, w h i l e o t h e r s may show
b o t h e f f e c t s , t h a t is, a c o m b i n a t i o n o f a n o d i c and
c a t h o d i c i n h i b i t i o n in v a r y i n g d e g r e e s .
Therefore,
w h i l e the c o r r o s i o n p o t e n t i a l may g i v e a p r e l i m i n a r y
i n d i c a t i o n o f the i n h i b i t o r mechanism, p o l a r i z a t i o n
c u r v e s s h o u l d be r e c o r d e d f o r more complete assessment
o f i t s mode o f a c t i o n .
T h i s is a l l the more important
s i n c e a r e d u c t i o n o f the a n o d i c r e a c t i o n r a t e , f o r ins t a n c e , c o u p l e d w i t h an a c c e l e r a t i o n o f the c a t h o d i c
r e a c t i o n r a t e may r e s u l t in a l a r g e c a t h o d i c p o t e n t i a l
s h i f t w i t h no change in t h e o v e r a l l c o r r o s i o n r a t e .
C o n v e r s e l y , i f b o t h a n o d i c an c a t h o d i c r e a c t i o n r a t e s
a r e r e d u c e d t o the same e x t e n t as shown in Fig.M- no
s h i f t in t h e c o r r o s i o n p o t e n t i a l is o b s e r v e d w h i l e the
i n h i b i t i o n e f f e c t is the l a r g e s t p o s s i b l e . T a b l e 2 i l -

9. HAUSLER
Corrosion
273
Inhibition
't
an F
7Q
= l
a
V
e x
'
^RT
(l-a)n F
\_i =-i -exp(-
V '- ' c
e E
Wt
'ext
an F
'corr L Pl" RT
-(l-)n F
c
Figure 1. Anodic and cathodic current-potential

system
/-Tâ
RT ^corr'J
^corr " E X P < K
ex
rehtionships in a corroding
+ blog i + i R
Q
//
//
//
./
//
/
^ ^ 7
\^77
,0
ext =
!
= a + blog i
= a'+ b'log i
' + b'log i + i R
c
Wr
W ^ P ^ ^ o f r ^ a ^ ' ^ p f ^ ^ H o r r " ^
Figure 2.
Effect of electrolyte resistance

CORROSION
CHEMISTRY

HAUSLER
Corrosion
Inhibition

CORROSION
276
CHEMISTRY
Table I I
WEIGHT LOSS MEASUREMENTS OF CARBON STEEL IN 10% SULFUR
IC ACID AS A FUNCTION OF TYPE AND CONCENTRATION OF IN
HIBITOR AT 2 5 C.
Inhibitor
C o n c e n t r a t i o n Weight l o s s C o r r o s i o n
of I n h i b i t o r
mg/2 5cm .
Potential
(mol/1)
day
mV v s . H
2
Blank
0
Aniline
0.0063
Diethylaniline
^
0.0063
p-Phenylene diamine
0.0 06 3
3-Naphthyl-amine
sat.sol
Phenyl--naphthyl amin
Pyridine
0.0063
Quinoline
0. 063
Quinoline
0.0063
â-Naphthoquinoline
0.063
a-Naphthoquinoline
0063
-Naphthoquinoline
063
-Naphthoquinoline
0063
2,4,-Dimethylquinoline
063
2,4,-Dimethylquinoline
, 0063
2,6-Dimethylquinoline
, 063
2,6-Dimethylquinoline
E t h y l q u i n o l i n i u m bromide0.0063
Acridine
sat.sol.
A c r i d i n e orange
sat.sol.
Acridine red
sat.sol.
Acriflavine
sat.sol.
Water s o l u b l e P e t r o l e u m
sat.sol.
sulfonate
sat.sol
Sulfonated o i l
sat.sol.
Commercial I n h i b i t o r A
sat.sol.
C sat.sol.
D sat.sol.
956
943
513
886
374
235
233
209
225
210
370
122
78
59
73
58
321
178
175
64
63
404
24
61
112
201
181
177
172
178
172
192
176
192
170
184
227
201
184
196
170
23
23
44
85
51
212
227
227
216
218
223

9.
HAUSLER
Corrosion
Inhibition
277
lustrtes t h e s e p o i n t s in a s u r v e y o f p o t e n t i a l s h i f t s
and c o r r o s i o n r a t e s f o r v a r i o u s i n h i b i t o r s on carbon
s t e e l in s u l f u r i c a c i d .
Such r e l a t i v e l y simple e l e c t r o c h e m i c a l t e c h n i q u e s t h e r e f o r e can be c o n s i d e r e d u s e f u l t o o l s f o r the r a p i d assessment o f i n h i b i t o r a c t i v i t y and f o r the purpose o f o b t a i n i n g p r e l i m i n a r y inf o r m a t i o n on a p o s s i b l e i n h i b i t i o n mechanism. Howe v e r , p o l a r i z a t i o n measurements, e i t h e r in the form o f
" L i n e a r p o l a r i z a t i o n measurements" o r T a f e l - s l o p e det e r m i n a t i o n s are f r a u g h t w i t h p e r i l ( c . f . H a u s l e r 11).
Even i f a system is r e l a t i v l y w e l l behaved, the i n f o r m a t i o n a l v a l u e o b t a i n e d from p o l a r i z a t i o n curves is
r e l a t i v e l y s m a l l and s h o u l d be combined w i t h more ext e n s i v e d e t e r m i n a t i o n o f the e l e c t r o d e k i n e t i c parameters,
a d s o r p t i o n s t u d i e s and mass t r a n s f e r s t u d i e s
in o r d e r t o e l u c i d a t e the mechanism o f a p a r t i c u l a r
corrosion inhibitor
inhibitive effects
t i o n o f the i n t e r p h a s e c h e m i s t r y w i l l e v e n t u a l l y l e a d
t o the p r e d i c t i v e c r i t e r i a f o r i n h i b i t o r b e h a v i o r .
Very few such i n v e s t i g a t i o n s have been c a r r i e d out
in the p a s t .
I t appears t h a t i n v e s t i g a t o r s were
m o s t l y s a t i s f i e d w i t h d e m o n s t r a t i n g the i n h i b i t o r y
e f f e c t o f c h e m i c a l s u b s t a n c e s and s u b s e q u e n t l y f o r c i n g
t h o s e s u b s t a n c e s i n t o one o r the o t h e r s i m p l e mechani s t i c concepts.
The few i n v e s t i g a t i o n s which have
p i n p o i n t e d v a s t l y more complex b e h a v i o r , have m o s t l y
been o v e r l o o k e d .
In the i n t e r e s t o f s t i m u l a t i n g more
r e s e a r c h in the f i e l d o f i n h i b i t o r chemistry, t h i s r e view s h a l l s t r e s s the more e x o t i c i n v e s t i g a t i o n s .
In
p a r t i c u l a r i t w i l l be s u g g e s t e d t h a t c h e m i c a l r e a c t i o n s
o f i n h i b i t o r s o c c u r i n g in the i n t e r p h a s e between c o r r o s i o n p r o d u c t s and the i n h i b i t o r are a more g e n e r a l
and w i d e s p r e a d phenomenon t h a n has g e n e r a l l y been bel i e v e d in the p a s t .
I n h i b i t i o n By T h i o u r e a And
Quinoline
Derivatives
A l a r g e number o f i n v e s t i g a t i o n s in a c i d media
have l e d t o the c o n c l u s i o n t h a t the i n h i b i t i o n e f f e c t
caused by r e l a t i v e l y s m a l l and s i m p l e m o l e c u l e s is due
t o t h e i r a d s o r p t i o n on the m e t a l s u r f a c e .
Compounds o f
t h i s n a t u r e u s u a l l y c o n t a i n s u l f u r and n i t r o g e n , o r are
o f the groups o f h i g h e r a l k y l - a l c o h o l s and f a t t y a c i d s .
T y p i c a l compounds t o be d i s c u s s e d h e r e in more d e t a i l
are q u i n o l i n e and t h i o u r e a d e r i v a t i v e s . F i g . 5 shows
a comparison of the e f f e c t i v e n e s s o f s e v e r a l such
compounds determined by means o f weight l o s s measurements on carbon s t e e l in 5% s u l f u r i c a c i d at 40 C.
as a f u n c t i o n o f the i n h i b i t o r c o n c e n t r a t i o n .
A cur-


10
10
10
Inhibitor Concn (mol/l)
-4
10
10
Springer-Verlag
0.25
0.50
0.75
1.00
Jf
ure 5. Weight loss of 0.1%C-steel in 5% aqueous H SO at 40C as a function of concen

tration of various quinoline and thiourea inhibitors (3)
10
Ethyl-thiourea
m-tolylthiourea
o- S p-tolylthiourea ~"
Methyl-thioure
Thiourea
Quinoline
2,6-Dimethyl-quinoline
N-ethyl-quinoline
- & -naphthoquinoline
9.
HAUSLER
Corrosion
Inhibition
279
s o r y e x a m i n a t i o n o f F i g . 5 might l e a d t o t h e c o n c l u s i o n
t h a t the r e l a t i o n s h i p s o f c o r r o s i o n r a t e v s . i n h i b i t o r
c o n c e n t r a t i o n are b a s i c a l l y q u i t e s i m i l a r f o r t h e two
c l a s s e s o f compounds and d i f f e r o n l y q u a n t i t a t i v e l y
w i t h r e s p e c t t o the e f f i c i e n c y .
I t w i l l be shown how
e v e r , t h a t t h e r e are indeed p r o f o u n d d i f f e r e n c e s be
tween the two c l a s s e s o f i n h i b i t o r s .
Hoar and H o l i d a y
(12) found r e l a t i v e l y simple c o n d i t i o n s as a r e s u l t o f
t h e i r i n v e s t i g a t i o n o f the c o r r o s i o n i n h i b i t i o n o f i r o n
in 5% s u l f u r i c a c i d by 2 , 6 - d i m e t h y l q u i n o l i n e .
These
a u t h o r s determined f i r s t the e x t e r n a l c u r r e n t - p o t e n t i a l
c u r v e s in the u n i h i b i t e d s o l u t i o n and t h e n the a n o d i c
p a r t i a l c u r r e n t - p o t e n t i a l c u r v e s at d i f f e r e n t i n h i b i
t o r c o n c e n t r a t i o n s and the q u a n t i t y o f d i s s o l v e d i r o n
in t h e e l e c t r o l y t e at c e r t a i n e l e c t r o d e p o t e n t i a l s .
The d i f f e r e n c e between t h e a n o d i c e x t e r n a l c u r r e n t and
the i n d e p e n d e n t l y determine
( d i s s o l v e d Fe) is th
The r e s u l t s as o b t a i n e d by Hoar and H o l i d a y are shown
in F i g . 6 .
The dashed curve r e p r e s e n t s the e x t e r n a l
p o l a r i z a t i o n b e h a v i o r in the absence o f i n h i b i t o r and
the b l a c k l i n e s are the T a f e l s l o p e s f o r the a n o d i c
p a r t i a l c u r r e n t d e n s i t y (the m e t a l d i s s o l u t i o n ) f o r
different i n h i b i t o r concentrations.
The c a t h o d i c p a r
t i a l c u r r e n t d e n s i t y (hydrogen e v e o l u t i o n ) is found f o r
a l l v a l u e s o f the i n h i b i t o r c o n c e n t r a t i o n s in the shad
ed a r e a .
T h e r e f o r e , i t is o b v i o u s t h a t the i n h i b i t o r
in t h i s case a c t s e x c l u s i v e l y by r e d u c i n g the a n o d i c
r e a c t i o n r a t e but not the c a t h o d i c one.
Kaesche and Hackerman (13) have i n v e s t i g a t e d the
i n h i b i t i o n o f s e v e r a l a l i p h a t i c and a r o m a t i c amines on
pure i r o n c o r r o d i n g in IN
hydrochloric acid.
These
a u t h o r s o b s e r v e d in t h i r t e e n out o f f o u r t e e n cases t h a t
the i n h i b i t i o n was b o t h a n o d i c and c a t h o d i c , a l b e i t
predominantly anodic.
The e x c e p t i o n was methylamine
which a c t e d o n l y c a t h o d i c a l l y . In the case o f the c o r
r o s i o n i n h i b i t i o n on pure i r o n by -naphthoquinoline in
sodium s u l f a t e / s u l f u r i c a c i d s o l u t i o n
one o b s e r v e s
a simple p a r a l l e l s h i f t o f the a n o d i c and c a t h o d i c
T a f e l l i n e s towards s m a l l e r v a l u e s o f c u r r e n t d e n s i t y .
Here the e f f e c t is almost s y m e t r i c a l , i n d i c a t i n g t h a t
t h i s i n h i b i t o r a c t s t o t h e same e x t e n t upon a n o d i c and
c a t h o d i c r e a c t i o n r a t e s . T h e r e f o r e , the e f f e c t o f
3 - n a p h t h o q u i n o l i n e can be e x p l a i n e d on t h e b a s i s t h a t
i t s a d s o r p t i o n b l o c k s a f r a c t i o n o f the m e t a l s u r f a c e
f o r a l l electrode r e a c t i o n s . I f equation 9 describes
the e x t e r n a l p o l a r i z a t i o n b e h a v i o r in terms o f a f u n c
t i o n o f the p a r t i a l c u r r e n t p o t e n t i a l r e l a t i o n s h i p f o r
the a n o d i c and c a t h o d i c r e a c t i o n s in the u s u a l terms:

280
CORROSION
-024
CHEMISTRY
-022 -0.20 -0.18 -0.16 -0.14
Potential vs. nH (V)

2
Springer-Verlag
Figure 6.
Current-potential diagram for 0.1 % C-steel in 5% aqueous ^0^ at

40C for various concentrations of 2,6-dimethylquinoline (3)

9.
HAUSLER
( i
Corrosion
281
Inhibition
ext o=iiI o- ' P[ /(Ban>o]- cath>o>
( i
*Pi- < cath>o!

e /
<>
where: i = exchange c u r r e n t d e n s i t y
= electrode potential
B
= anodic T a f e l slope
cath
cathodic T a f e l slope
t h e n e q u a t i o n 10 d e s c r i b e s the p o l a r i z a t i o n
i n h i b i t e d e l e c t r o d e s in the same terms:
a n
( i e x t >I=(i >I
n
e x
behavior
P I ' < a n > i H i c a t h >I

(
^-{^^cath^f
I f the i n h i b i t o r doe
-naphthoquinoline)
(B
of
an>o = < B
a n
affect
(B
i ;
th
Tafel
= (B
c a
slope
th)l
(se
<H>
the i n h i b i t e d a n o d i c c u r r e n t d e n s i t y is a simple f r a c
t i o n o f the u n i n h i b i t e d a n o d i c c u r r e n t d e n s i t y as shown
in e q u a t i o n 12.
( i an ) ! = ( ian ) (1-)
a n
and
f o r the
(12)
cathodic
partial
current
<icath>I = <icath>
( 1
"
( 1 3 )
I t f o l l o w s t h a t the i n h i b i t e d e x t e r n a l c u r r e n t is a
s i m i l a r f r a c t i o n o f the u n i n h i b i t e d e x t e r n a l c u r r e n t
as i n d i c a t e d in e q u a t i o n 14
( i
e x t > I = <iext>o
<1">
I t a l s o f o l l o w s t h a t the degree of i n h i b i t i o n in
case is d i r e c t l y p r o p o r t i o n a l t o the f r a c t i o n o f
s u r f a c e c o v e r e d w i t h adsorbed i n h i b i t o r :
ôrr
P=
ligh
this
the
=9
(15)
T O
1
corr
In g e n e r a l , however, t h e s e e q u a t i o n s are not a p p l i c a b l e
s i n c e s y m m e t r i c a l a n o d i c and c a t h o d i c i n h i b i t i o n is a
r a r e case.
In the case o f d i m e t h y l q u i n o l i n e w h i c h , as
shown in F i g . 6 , does not a f f e c t the c a t h o d i c hydrogen
e v o l u t i o n , Hoare and H o l i d a y (1?)
have proposed a
d i f f e r e n t approach.
One can assume t h a t two k i n d s o f

CORROSION
282
CHEMISTRY
a t o m i c s i t e s o c c u r on the s t e e l s u r f a c e . There might

be a s i t e S]_ o c c u r r i n g at a f r e q u e n c y N]_ where the
a n o d i c m e t a l d i s s o l u t i o n o c c u r s , and a l l o t h e r s i t e s ,
S2 o c c u r r i n g w i t h a f r e q u e n c y N .
One f u r t h e r assumes
t h a t N-L is much s m a l l e r than N2 and t h a t the c a t h o d i c
hydrogen e v o l u t i o n o c c u r s on a l l s i t e s S-^ and S .
Ads o r p t i o n now o c c u r s t o a d i f f e r e n t degree on the s i t e s
w i t h a coverage 9-j_ and a coverage 9 on the s i t e s
S .
I f we then f u r t h e r n e g l e c t the c a t h o d i c hydrogen
e v o l u t i o n on the s i t e s S i because o f t h e i r n e g l i g i b l e
c o n t r i b u t i o n , equation lb r e s u l t s :
t
(iextl = <*2>
( 1
" 1
e x
pf
/ ( B
a n > J " (igat>o'
(l-9 ) exp|-e/(B
2
c a t h
) |
0
(16)
Since dimethylquinolin
i n h i b i t o r i t is p r o b a b l
sorbed.
One can f u r t h e r s p e c u l a t e t h a t the a d s o r p t i o n
o c c u r s o n l y on the s i t e s S-, , t h a t is the l a t t i c e d i s
s o l u t i o n s i t e s which w i l l f a v o r the a d s o r p t i o n o f
f o r e i g n m o l e c u l e s from an e n e r g e t i c p o i n t o f view.
T h e r e f o r e , 9 w i l l be a p p r o x i m a t l y z e r o .
E q u a t i o n 16
then reduces t o e q u a t i o n 17:
2
(i
ext>I = (iaVo
( 1
- 1
e x
PI
e 1 (B
an>ci "
'igathV
expj-e/(B
c a t h
) j
0
(17)
By p r o p e r adjustment o f the parameter 9-j_ the curves in

F i g . 6 can then be c a l c u l a t e d .
S i m i l a r c a l c u l a t i o n s have been c a r r i e d out f o r the
i n h i b i t i o n of i r o n c o r r o s i o n in h y d r o c h l o r i c a c i d by
V i c t o r i a b l u e which, a c c o r d i n g t o E l z e and F i s c h e r (14)
does not a f f e c t the T a f e l s l o p e s , but reduces both the
a n o d i c and c a t h o d i c p a r t i a l r e a c t i o n s t o a d i f f e r e n t
degree.
In t h i s p a r t i c u l a r case ]_ and 9 have t o be
a d j u s t e d by way o f a t r i a l and e r r o r c a l c u l a t i o n .
T h i s simple model o f the i n h i b i t o r a c t i o n which
is based e s s e n t i a l l y on the p o t e n t i a l independence o f
the i n h i b i t o r a d s o r p t i o n is, however, o f t e n not ap
plicable.
Kaesche (15) i n d i c a t e s t h a t the c o r r o s i o n
i n h i b i t i o n o f pure i r o n in s u l f u r i c o r p e r c h l o r i c a c i d
by p h e n y l - t h i o u r e a s t r o n g l y a f f e c t s the s l o p e s o f the
p o l a r i z a t i o n c u r v e s , l e a v i n g the c o r r o s i o n p o t e n t i a l s
almost unchanged F i g . 7 .
In f a c t , the p o l a r i z a t i o n
curves f o r the i n h i b i t e d s i t u a t i o n do not e x h i b i t r e a l
T a f e l behavior.
This behavior f i n d s a p a r t i a l explan
a t i o n in the f a c t t h a t the mechanism o f the hydrogen
e v o l u t i o n appears t o be changed in the p r e s e n c e o f
2

9.
HAUSLER
Corrosion
Inhibition
283
p h e n y l t h i o u r e a . S p e c i f i c a l l y , i t appears the e l e c t r o
c h e m i c a l d e s o r p t i o n o f hydrogen is g r e a t l y h i n d e r e d .
T h i s mechanism may p o s s i b l y f i n d c o n f i r m a t i o n in the
i n d e p e n d e n t l y o b s e r v e d f a c t t h a t in the p r e s e n c e of
p h e n y l t h i o u r e a c o n s i d e r a b l y more hydrogen d i f f u s e s i n t o
the m e t a l . However, the i n h i b i t i o n mechanism o f p h e n y l t h i o u r e a is p r o b a b l y c o n s i d e r a b l y more c o m p l i c a t e d t h a n
t h a t , as can be seen from the v e r y complex r e l a t i o n
s h i p o f the c o r r o s i o n p o t e n t i a l w i t h the i n h i b i t o r con
centration.
T h i s is shown in F i g . 8 , in comparison
with a s i m i l a r r e l a t i o n s h i p f o r
g-naphthoquinoline.
Hoar (16) found t h a t in the c o r r o s i o n i n h i b i t i o n o f
i r o n in h y d r o c h l o r i c a c i d by -naphthoquinoline, the
c o r r o s i o n p o t e n t i a l i n c r e a s e s m o n o t o n i c a l l y w i t h in
c r e a s i n g i n h i b i t o r c o n c e n t r a t i o n , w h i l e in the case of
o - t o l y l t h i o u r e a one o b s e r v e s f i r s t a d e c r e a s e of the
corrosion potentia
i n h i b i t o r concentrations
h i b i t i o n o f the c a t h o d i c p a r t i a l r e a c t i o n at s m a l l in
h i b i t o r c o n c e n t r a t i o n s is e x h i b i t e d a l s o by
phenylt h i o u r e a a c c o r d i n g t o Kaesche.
F u r t h e r m o r e , in the
s e r i e s o f the t h i o u r e a d e r i v a t i v e s one o f t e n f i n d s c o r
r o s i o n a c c e l e r a t i o n at s m a l l c o n c e n t r a t i o n s , as f o r in
s t a n c e in the case o f p h e n y l t h i o u r e a at c o n c e n t r a t i o n s
o f 10moles per l i t e r .
T h i s appears t o be due t o a
s m a l l c a t h o d i c d e c o m p o s i t i o n of t h i o u r e a and i t s de
r i v a t i v e s in the course of which hydrogen s u l f i d e is
formed. As is w e l l known, hydrogen s u l f i d e tends t o
a c c e l e r a t e c o r r o s i o n , in p a r t i c u l a r the a n o d i c p a r t i a l
r e a c t i o n o f d i s s o l u t i o n o f i r o n , which has been demon
s t r a t e d i n d e p e n d e n t l y by o t h e r a u t h o r s (17).
I t is g e n e r a l l y assumed t h a t i o n s which can a c c e l
e r a t e e i t h e r o r both p a r t i a l r e a c t i o n s in a c o r r o s i o n
p r o c e s s are c a p a b l e of b e i n g adsorbed on the i r o n s u r
face.
Thus i t is known t h a t hydrogen s u l f i d e i o n s
which a c c e l e r a t e both p a r t i a l r e a c t i o n s o f a c i d c o r
r o s i o n ( a l t h o u g h p r e d o m i n a n t l y the a n o d i c o n e ) , and
f o r m i c a c i d m o l e c u l e s which c a t a l y z e the c a t h o d i c p a r
t i a l r e a c t i o n but i n h i b i t the a n o d i c one, as w e l l as
commercial i n h i b i t o r s which r e d u c e both p a r t i a l r e
a c t i o n s , are in f a c t adsorbed on the i r o n s u r f a c e .
As
a consequence the mere f a c t t h a t a d s o r p t i o n t a k e s p l a c e
cannot be used t o p r e d i c t an e x p e c t e d change in c o r
r o s i o n r a t e as i t is a l s o known t h a t h a l i d e i o n s c a t a l i z e the a n o d i c d i s s o l u t i o n o f i n d i u m , w h i l e hydroxy1
a d s o r p t i o n c a t a l y z e s the a n o d i c d i s s o l u t i o n of i r o n .
F u r t h e r m o r e , i t is a l s o known t h a t c e r t a i n i o n s can
act e i t h e r as a c a t a l y s t o r an i n h i b i t o r when a d s o r b
ed on the m e t a l s u r f a c e depending on the type of m e t a l
considered.
K o l o t y r k i n (IB) o b s e r v e d t h a t the a d s o r p -

CORROSION CHEMISTRY
284
4000
-0.45
-0.40 -035 -030 -0.25
Electrode Potential (V)

SpringerVerlag
Figure 7. Poforization of carbonyl iron in IN NaClO^/HClO^ at pH 2, 25C
deaerated, with and without 7 10~ mol/L phenylthiourea (3)
5
/3-Naphthoqulnollne
o-tolyl-thlourea
Springer-Verlag
Figure 8. Weight loss and rest potential
of mild steelin10% H SO as a function
of the concentration of -naphthoquinoline and o-tolylthiourea (3)
z
Inhibitor Concn (10 mol/l)

9.
HAUSLER
Corrosion
Inhibition
285
t i o n o f i o d i n e i o n s c o n s i s t e n t l y i n c r e a s e s the hydrogen
o v e r - v o l t a g e on s i l v e r but d e c r e a s e s i t on mercury.
On
l e a d one o b s e r v e s t h a t s m a l l amounts o f adsorbed i o d i n e
i n c r e a s e the hydrogen o v e r - p o t e n t i a l , l a r g e r amounts,
however, d e c r e a s e i t . In the case o f the hydrogen evo l u t i o n i t is p r o b a b l y the h e a t o f a d s o r p t i o n o f the
atomic hydrogen on a p a r t i c u l a r m e t a l which c o n t r o l s
the a c c e l e r a t i o n or i n h i b i t i o n o f t h i s r e a c t i o n upon
a d s o r p t i o n o f a f o r e i g n i o n . With r e s p e c t t o the
k i n e t i c s o f the a n o d i c d i s s o l u t i o n o f m e t a l , however,
the i m p o r t a n t parameter is most l i k e l y the s t r e n g t h o f
the complex f o r m a t i o n between s u r f a c e m e t a l atoms and
the adsorbed p a r t i c l e .
I f the complex f o r m a t i o n is
weak, t h e r e f o r e h a r d l y a f f e c t i n g the bonding f o r c e s
h o l d i n g the s u r f a c e atoms in the m e t a l l a t t i c e , one
would e x p e c t i n h i b i t i o n t h r o u g h simple b l o c k i n g o f the
dissolution sites.
Conversely
a c t between the s u r f a c
p a r t i c l e , one would e x p e c t c a t a l y s i s o f the m e t a l d i s solution.
A l o n g t h e s e l i n e s one a l s o has t o c o n s i d e r
the p o s s i b i l i t y t h a t one k i n d o f adsorbed p a r t i c l e
can
be d i s p l a c e d by a d i f f e r e n t k i n d .
One would t h e r e f o r e
suggest t h a t i n c r e a s i n g the c o n c e n t r a t i o n o f t h i o u r e a
d e r i v a t i v e s e v e n t u a l l y leads to c o r r o s i o n i n h i b i t i o n
because of c o m p e t i t i v e a d s o r p t i o n w i t h the hydrogen
s u l f i d e i o n which causes a c c e l e r a t i o n o f c o r r o s i o n .
A c c e l e r a t i o n of c o r r o s i o n has been demonstrated
w i t h s t r o n g complexing agents such as EDTA s a l t s .
Howe v e r , as EDTA is s u b s t i t u t e d w i t h l o n g e r a l k y l c h a i n s ,
the c a t a l y t i c e f f e c t is g r a d u a l l y l o s t and i n h i b i t i o n
is o b t a i n e d .
T h i s s t r o n g l y s u g g e s t s t h a t the a d s o r p t i o n o f the i n h i b i t o r p a r t i c l e on the m e t a l s u r f a c e ,
a p u r e l y i n t e r f a c i a l phenomenon, is not the predominant
f e a t u r e t o be s t u d i e d , but t h a t in f a c t the c h e m i s t r y
in the i n t e r p h a s e , in p a r t i c u l a r , the f o r m a t i o n o f
c o r r o s i o n p r o d u c t s and c o r r o s i o n p r o d u c t l a y e r s has t o
be g i v e n more c o n s i d e r a t i o n .
A case in p o i n t is a study made by Ross (JJ) on the
d i s s o l u t i o n o f i r o n in 0.5 m o l a r s u l f u r i c a c i d in the
p r e s e n c e o f t h i o u r e a at 40 C. The r e s u l t s o f t h i s
s t u d y , which was conducted as a f u n c t i o n o f the f l o w
r a t e , are shown in F i g . 9 .
I t appears t h a t the u n i n h i b i t e d d i s s o l u t i o n o f i r o n f o l l o w s e x p e c t e d mass t r a n s f e r b e h a v i o r b o t h in the l a m i n a r and t u r b u l e n t r e g i o n s .
However, at two i n h i b i t o r c o n c e n t r a t i o n s marked d e v i a t i o n s from the e x p e c t e d mass t r a n s f e r b e h a v i o r are observed.
Ross attempted t o e x p l a i n t h e s e r e s u l t s on
the b a s i s t h a t d i f f e r e n t i n h i b i t o r c o n c e n t r a t i o n s a f f e c t the a n o d i c and c a t h o d i c p o l a r i z a t i o n in d i f f e r e n t
ways, t a k i n g a l s o i n t o c o n s i d e r a t i o n t h a t at s m a l l

286
CORROSION

CHEMISTRY
9.
HAUSLER
Corrosion
Inhibition
287
t h i o u r e a c o n c e n t r a t i o n s hydrogen s u l f i d e is formed on
the s u r f a c e o f the m e t a l c a t a l i z i n g the a n o d i c r e a c t i o n , t h e r e b y a c h i e v i n g a c o r r o s i o n r a t e which is
h i g h e r t h a n the b l a n k c o r r o s i o n r a t e .
However, R o s s s
e x p l a n a t i o n l e a v e s many ends u n t i e d .
One has t o exp l a i n f i r s t o f a l l the mass t r a n s f e r b e h a v i o r f o r the
u n i n h i b i t e d d i s s o l u t i o n o f i r o n in s u l f u r i c a c i d .
At
a p r o t o n c o n c e n t r a t i o n o f one normal and at c o r r o s i o n
r a t e s as measured, p r o t o n d i f f u s i o n cannot be r a t e controlling.
Second,the i r o n d i f f u s i o n away from the meta l s u r f a c e is not e x p e c t e d t o be r a t e l i m i t i n g , s i n c e
i r o n can in f a c t d i f f u s e away from the s u r f a c e as f a s t
as i t is formed, a f a c t t h a t has been e x p e r i m e n t a l l y
v e r i f i e d by t h i s a u t h o r (see b e l o w ) .
One must t h e n
assume t h a t the o b s e r v e d mass t r a n s f e r b e h a v i o r is
caused by a secondary r e a c t i o n most l i k e l y the d i s s o l u t i o n of a c o r r o s i o
t a i n i r o n s u l f a t e s ar
as the monohydrate o f the f e r r o u s s u l f a t e , and f e r r i c
sulfate.
In R o s s s experiment oxygen was
present
s i n c e the a u t h o r does not mention any p r e c a u t i o n s f o r
k e e p i n g oxygen out o f the e x p e r i m e n t a l system.
At low t h i o u r e a c o n c e n t r a t i o n s ( 2 1 0 ~ m o l a r ) i t
is o b s e r v e d t h a t the c o r r o s i o n r a t e v a r i e s approximatel y w i t h the 1/5 power o f the f l o w r a t e .
This author
has o b s e r v e d t h a t , in hydrogen s u l f i d e s a t u r a t e d s o l u t i o n s at 70 C in the p r e s e n c e o f s m a l l amounts o f
ammonium c h l o r i d e * the c a t h o d i c p a r t i a l r e a c t i o n f o r
i r o n c o r r o s i o n v a r i e s w i t h the l / 6 t h power o f the f l o w
rate.
T h i s maybe a c o i n c i d e n c e ; however, s i n c e the
f o r m a t i o n o f hydrogen s u l f i d e and i r o n s u l f i d e on
c o r r o d i n g i r o n s u r f a c e s in a c i d t h i o u r e a c o n t a i n i n g
media has been o b s e r v e d i n d e p e n d e n t l y by o t h e r a u t h o r s ,
i t is q u i t e l i k e l y t h a t the abnormal mass t r a n s f e r beh a v i o r o b s e r v e d by Ross f o r the s m a l l t h i o u r e a concent r a t i o n is in f a c t caused by an i r o n s u l f i d e l a y e r on
the s u r f a c e o f the m e t a l .
At h i g h e r t h i o u r e a concent r a t i o n s t h e r e may w e l l be c o m p e t i t i o n between the
t h i o u r e a m o l e c u l e and the hydrogen s u l f i d e in the
comp l e x i n g r e a c t i o n w i t h i r o n . I t s h o u l d be n o t e d , t h a t
the next h i g h e r t h i o u r e a c o n c e n t r a t i o n is t h r e e o r d e r s
o f magnitude l a r g e r but a c h i e v e s o n l y a m a r g i n a l inhibition effect.
One would t h e r e f o r e assume t h a t
t h i o u r e a is in c o m p e t i t i o n w i t h s u l f a t e or water f o r
l i g a n d p o s i t i o n s around the i r o n . S i n c e t h i o u r e a is a
n e u t r a l molecule, i t is q u i t e u n d e r s t a n d a b l e t h a t i t
w i l l reduce the d i s s o l u t i o n r a t e o f i r o n s u l f a t e merely
by b l o c k i n g a c c e s s o f water m o l e c u l e s t o the i r o n s u l fate surface.
A complete e x p l a n a t i o n o f Ross's s c a n t y
d a t a is c o m p l i c a t e d by the p r e s e n c e of oxygen which
1

CORROSION
288
CHEMISTRY
w i l l i n t e r f e r e w i t h the c o r r o s i o n and complexing r e a c

t i o n s on the s u r f a c e o f the m e t a l .
Nevertheless,
this
p a r t i c u l a r i n v e s t i g a t i o n is o f g r e a t v a l u e in t h a t i t
p o i n t s out the importance o f s t u d y i n g i n h i b i t o r e f f e c
t i v e n e s s under dynamic flow c o n d i t i o n s , and in under
l i n i n g f u r t h e r the importance o f the c h e m i s t r y o c c u r
r i n g in a phase immediately a d j a c e n t t o the m e t a l s u r
f a c e but d i s t i n c t l y d i f f e r e n t from the b u l k of the
c o r r o s i v e medium.
Acetylenic Inhibitors
A c e t y l e n i c compounds have l o n g been known as e f
f e c t i v e - c o r r o s i o n i n h i b i t o r s in h y d r o c h l o r i c a c i d .
T e d e s c h i and coworkers (20,21) have p r e s e n t e d o v e r the
p a s t 10 y e a r s e x t e n s i v e i n v e s t i g a t i o n s o f t h e s e com
pounds. T h e i r r e s u l t
and 5.
Some o f the
sons are the p o s i t i o n o f the h y d r o x y l group and the po
s i t i o n o f the t r i p l e bond. Thus i t appears t h a t the hy
d r o x y l group has t o be in -position t o the a c e t y l e n i c
f u n c t i o n and optimum e f f i c i e n c y is o b t a i n e d i f the
a c e t y l e n i c f u n c t i o n is t e r m i n a l .
These two e f f e c t s can
be e x p l a i n e d on the b a s i s o f the tautomerism shown in
e q u a t i o n 18.
(18)
T h i s f o r m a l i s m i m p l i e s t h a t the p o l a r i z a t i o n o f
the t r i p l e bond can be s t a b i l i z e d f i r s t by a n o n c l a s s i c a l carbonium i o n and f u r t h e r by an -keto-double bond
c o n f i r g u r a t i o n which is known t o complex s t r o n g l y w i t h
t r a n s i t i o n metal ions.
I t is n o t e d t h a t the h y d r o x y l
group has t o be l o c a t e d not o n l y in -position but on
a secondary carbon atom f o r s t r o n g c o r r o s i o n i n h i b i t i o n
to r e s u l t .
T h i s is t o be e x p e c t e d , s i n c e p r o t o n s are
much more apt t o form n o n c l a s s i c a l carbonium i o n s t h a n
m e t h y l groups.
However, i f the t e r m i n a l p r o t o n on the
t r i p l e bond is s u b s t i t u t e d w i t h a s t r o n g e l e c t r o p h i l i c
group,the p o l a r i z a t i o n o f the t r i p l e bond becomes
s t r o n g enough t o i n v o l v e the above i n d i c a t e d
tauto
merism.
One can f u r t h e r r a t i o n a l i z e t h a t a compound w i t h
a n o n - t e r m i n a l t r i p l e bond e x p e r i e n c e s some s t e r i c
h i n d r a n c e in the f o r m a t i o n of complexes w i t h t r a n s i
t i o n metal ions.
Thus, the e f f e c t i n d i c a t e d in T a b l e 3
which T e d e s c h i a s c r i b e d t o s t e r i c h i n d r a n c e is r a t h e r
a k i n e t i c e f f e c t c o n c e r n i n g the i n t r a - m o l e c u l a r s h i f t s

Corrosion
9. H A U S L E R
289
Inhibition
Table I I I
Decreasing
1. L o c a t i o n o f T r i p l e
R
R]_
Rl
= CH ^C H
3
OH
R]_ = H or CH
R
Bond:
r
2
Inhibition
1 1
2. S t e r i c h i n d r a n c e
H
H6C=CH>
OH
"
A_
c = c
OH "
OH
_ =c_c_
c
"
H
CH 6C=CH>>
H
3
R
~2
OH
CH C=CH
3
OH
3. A l k y l Chain Length:
H
R <jjC=CH
2
CH
N : H - > C H > CH
CH ^
o f T r i p l e Bond and H y d r o x y l F u n c t i o n :
R2: C H n > + > C H ,

5
4. P o s i t i o n
CH C H C H C H C = C H
3
CH C H C = C C H C H 0 H
3
OH
INHIBITOR
NO INHIBITOR

290
CORROSION
CHEMISTRY
T a b l e IV
Type C h a i n
Formula
OH
Length C o r r o s i o n Rate
OHCH C===CH
CH
OHCHC=CH
I
CH
CH CH CH CHC=CH
0. 026
>1.6
0. 002
OH
CHq
CH CHCH C=C
CHo
OH
3
Table V
Formula
H
lo
3
Temperature
C o n c e n t r a t i o n C o r r o s i o n Rate
C-
200
0.2
6H
175
0.3
0.221
>1.8
>1.8
<f 3
CH C=CCI
3
OH
CH
20 0
0. 2
175
0.3
0.243
200
175
0. 4
0.4
0. 004
0.002
17 5
0 .1
Some
CHbC=CI
6H
CH
3
C H -(C = C H
3
0[CH CH 0] H
2
Activity

9.
HAUSLER
Corrosion
291
Inhibition
n e c e s s a r y f o r complex f o r m a t i o n . I t i s a l s o i n t e r e s t
i n g t o note t h a t s u b s t i t u t e d p r o p a r g y l a l c o h o l s become
more e f f e c t i v e as the a l k y l c h a i n i n c r e a s e s .
This
e f f e c t most l i k e l y has t o do w i t h the n a t u r e o f t h e
"adsorbed l a y e r " i n t h a t i n c r e a s i n g l e n g t h o f the a l k y l
c h a i n i m p a r t s g r e a t e r h y d r o p h o b i c i t y t o the i n t e r f a c i a l
l a y e r , thus s q u e e z i n g out water m o l e c u l e s from the
interphase.
Q u a n t i t a t i v e r e s u l t s f o r t h i s e f f e c t are
shown i n T a b l e 4.
The temperature e f f e c t o f some a c e t y l e n i c d e r i v
atives
i s quite surprising. Dimethyl-propargyl
a l c o h o l l o s e s i t s e f f i c i e n c y as the temperature r i s e s
from 175 t o 200 F.
The f a c t t h a t t h i s i s no l o n g e r
t r u e f o r the i o d i n e - s u b s t i t u t e d compound i s i n s u p p o r t
of t h e above mechanism
Furthermore
i f the h y d r o x y l
group on the d i m e t h y
a p o l y o l group, th
l o s t , u n d e r l i n i n g the importance o f the h y d r o x y l group
as an i n t e g r a l p a r t o f t h e i n h i b i t i o n mechanism. I t
s h o u l d f u r t h e r be n o t e d , t h a t t h e e q u i v a l e n t compounds
c o n t a i n i n g double bonds i n s t e a d o f the t r i p l e bond
show no c o r r o s i o n i n h i b i t i o n whatsoever.
Tedeschi s
attempt t o f o r m a l i z e the i n h i b i t i o n mechanism o f
a c e t y l e n i c compounds has r e c e n t l y been p u b l i s h e d , (22)
and i s shown i n T a b l e 6.
Here the i n t e r a c t i o n o f p r o t o n a t e d a l k y n o l s such as m e t h y l - b u t y n o l and h e x y n o l
w i t h themselves and the m e t a l s u r f a c e i s i l l u s t r a t e d
i n the b u i l d i n g up o f a complex i n h i b i t o r m u l t i l a y e r .
Such a charged m o l e c u l a r b a r r i e r i s analogous t o a
t h r e e - d i m e n s i o n a l polymer i n which a l a r g e excess o f
p r o t o n s i s k e p t from t h e m e t a l by r e p u l s i o n o f l i k e
charges o r by i n t e r a c t i o n w i t h the b a s i c - f i e l d o f
the t r i p l e bond.
A c c o r d i n g t o P o l i n g (23) IR s t u d i e s have i n d i c a t e d
t h a t such f i l m s may be up t o 200 t h i c k .
I f the a v e r age m o l e c u l e i s e s t i m a t e d a t about 4 i n d i a m e t e r , t h e n
a b a r r i e r o f up t o f i f t y m o l e c u l e s t h i c k i s p o s s i b l e .
The a b i l i t y o f t h e t r i p l e bond t o f u n c t i o n as a Broens t e d base i n hydrogen bonding w i t h e i t h e r a c i d i c
e t h y n y l e p r o t o n s o r h y d r o x y l g r o u p s has a l s o been proved
by IR s t u d i e s C23).
The f o r m a t i o n o f such a space charge l a y e r i s i n t u i t i v e l y a p p e a l i n g , a l t h o u g h i t i s u n l i k e l y t o extend
v e r y f a r . I f p r o t o n s were t o p l a y a r o l e i n the b u i l d up o f a l a r g e t h r e e - d i m e n s i o n a l polymerous network o f
the k i n d shown i n T a b l e 6, t h e n n e c e s s a r i l y some nega t i v e c o u n t e r i o n s would have t o be b u i l t i n t o such a
layer.
However, a more s e r i o u s f l a w o f t h i s model i s
t h a t i t cannot account f o r t h e m i g r a t i o n o f two o r
three v a l e n t metal ions through
such a polymer l a y e r .
!

292
CORROSION
CHEMISTRY
T a b l e VI
Methyl Butynol
(MB) - H e x y n o l
( C H ) C G s = CH
3
(H)
CH (CH )2HC=CH
H+
OH
(MB)
H
C
?3 7
H
H0:H
HC==CC
C H2 )
, (3
3
H 0
2
(CH)
" H:9H
(CHo) GC^CH
HCaeCH
//
HC===C
""H : 0 H
C3
o H7
7
(C3
H ) 2- C, ~ C s C H
q
H:0H +
FORMATION OF POLYMEROUS LAYERS WITH

A C E T Y L E N I C COMPOUNDS I N HYDROCHLORIC
A C I D ON METAL SURFACES

9.
HAUSLER
Corrosion
Inhibition
293
In h y d r o c h l o r i c a c i d f o r i n s t a n c e a t room temperature
the c o r r o s i o n r a t e a t 9 5% i n h i b i t i o n i s s t i l l s e v e r a l
hundred mpy s.
T h e r e f o r e , u n d e r steady s t a t e con
d i t i o n s t h e r e i s a f l u x o f i r o n i o n s a c r o s s the i n t e r
phase which must be accommodated i n the i n h i b i t i o n mech
anism.
T h i s c o u l d be done more e a s i l y by assuming a
c o r r o s i o n p r o d u c t l a y e r o f d i s c r e t e t h i c k n e s s composed
o f a complex formed from m e t a l i o n s and i n h i b i t o r .
De
t a i l s o f t h i s model w i l l be d i s c u s s e d below.
Thus, i t i s i m p o r t a n t t o p o i n t out t h a t any model
o f the i n h i b i t i o n mechanism has t o i n c l u d e not o n l y an
e x p l a n a t i o n o f the i n t e r f e r e n c e w i t h the s u r f a c e
k i n e t i c s but a l s o w i t h the charge t r a n s f e r p r o c e s s e s
a c r o s s the boundry l a y e r .
The study o f such t r a n s f e r p r o c e s s e s was one o f
the purposes o f a f a i r l y e x t e n s i v e i n v e s t i g a t i o n o f the
i n h i b i t i o n of c o r r o s i o
acetylenic corrosio
t h i s i n v e s t i g a t i o n were: the c o n c e n t r a t i o n o f the
a c i d , the c o n c e n t r a t i o n o f the i n h i b i t o r , the f l o w r a t e
and the oxygen c o n c e n t r a t i o n i n the c o r r o s i v e medium.
While most o f the e x p e r i m e n t a l d a t a were o b t a i n e d by
means o f the so c a l l e d r e s i s t a n c e p r o b e , p o l a r i z a t i o n
measurements were c a r r i e d out i n o r d e r t o e l u c i d a t e
some o f the more p e c u l i a r r e s u l t s . The e x p e r i m e n t a l
arrangement i s more f u l l y e x p l a i n e d i n ( 2 4 ) .
O r i g i n a l l y i t had been i n t e n d e d t o f i n d a c o r
r e l a t i o n between i n h i b i t o r c o n s t i t u t i o n and i n h i b i t o r
activity.
The approach t a k e n i n e v a l u a t i n g the d a t a
e s s e n t i a l l y f o l l o w e d the t h i n k i n g o f o t h e r i n v e s t i g a
t o r s i n the f i e l d .
I t was assumed t h a t the parameters
o f an a d s o r p t i o n i s o t h e r m would be a means t o c o r r e
l a t e c h e m i c a l s t r u c t u r e w i t h i n h i b i t o r performance
f
(15.)
I f one assumes t h a t the b l a n k c o r r o s i o n r a t e

(I
) r e p r e s e n t s the t o t a l number o f " a c t i v e s i t e s "
on the s u r f a c e o f a c o r r o d i n g m e t a l and t h a t the i n
hibited corrosion rate ( i
) r e p r e s e n t s the t o t a l
c orr
number o f a c t i v e s i t e s minus the i n h i b i t e d s i t e s , t h e n
e q u a t i o n 15 i s an e x p r e s s i o n f o r t h e f r a c t i o n o f the
s u r f a c e which i s c o v e r e d by i n h i b i t o r m o l e c u l e s .
Thus,
as e x p l a i n e d p r e v i o u s l y , stands f o r t h e f r a c t i o n a l
coverage o f the s u r f a c e w i t h i n h i b i t o r and i s , o f
c o u r s e , e q u a l t o the p e r c e n t p r o t e c t i o n as d e f i n e d by
e q u a t i o n 15.
The dependence o f coverage on the con
c e n t r a t i o n o f the i n h i b i t o r , w i t h i n the assumptions and
r e s t r i c t i o n s made p r e v i o u s l y , i s g i v e n by the a d s o r p
t i o n isotherm of a p a r t i c u l a r i n h i b i t o r .
A t y p i c a l ad
s o r p t i o n i s o t h e r m was d e r i v e d by Langmuir and i s g i v e n
i n e q u a t i o n 19:
o r > r

294
CORROSION
Q =
1 +
C H E M I S T R Y
(19)
KC
i n h
where i s the Langmuir a d s o r p t i o n c o n s t a n t .

Rearrang
i n g e q u a t i o n s 15 and 19 g i v e e q u a t i o n 20, which shows
the r e l a t i o n s h i p between t h e p e r c e n t p r o t e c t i o n and
i n h i b i t o r concentration discussed e a r l i e r :
.
i
^ =
(20)
(1-P)
I t i s n e c e s s a r y t o d i s c u s s some o f the i n h e r e n t assump

t i o n s o f t h i s approach. I t has been p o i n t e d out e a r l i e r
t h a t an i n h i b i t o r doe
o d i c and c a t h o d i c r e a c t i o
are n o n e t h e l e s s u s e f u l i f the b l a n k c o r r o s i o n c u r r e n t
(I
) i s i n f a c t p r o p o r t i o n a l t o the t o t a l number o f
s i t e s t h a t can p o s s i b l y adsorb i n h i b i t o r .
T h i s , how
e v e r , i s not n e c e s s a r i l y so, as i t has been shown t h a t
o f t e n a s u b s t a n t i a l c o r r o s i o n r a t e i s observed a t s a t
u r a t i o n coverages by the i n h i b i t o r .
A number o f a d s o r p t i o n isotherms have been proposed
in
the
l i t e r a t u r e and have been used f o r such c o r
r e l a t i o n purposes.
Of t h e s e the Langmuir a d s o r p t i o n
i s o t h e r m shown i n e q u a t i o n s 19 and 20 i s the s i m p l e s t
one.
I t i s based on the assumption t h a t a l l s i t e s are
e n e r g e t i c a l l y e q u a l , t h a t i s the heat o f a d s o r p t i o n
i s independent o f c o v e r a g e .
I t can be seen from equa
t i o n 20 t h a t , i f the l o g a r i t h m o f the i n h i b i t o r concen
t r a t i o n i s p l o t t e d a g a i n s t the l o g a r i t h m o f P / ( l - P ) , a
s t r a i g h t l i n e with u n i t slope should r e s u l t .
Hence,
t h i s c r i t e r i o n can be used t o t e s t the Langmuir assump
tions .
A n o t h e r a d s o r p t i o n i s o t h e r m was d e r i v e d by
F r e u n d l i c h and i s shown i n e q u a t i o n 21.
Here the
l o g a r i t h m o f coverage i s d i r e c t l y p r o p o r t i o n a l t o the
l o g a r i t h m o f the i n h i b i t o r c o n c e n t r a t i o n .
This i s o
therm i s o n l y v a l i d a t low c o v e r a g e .
I t assumes ex
p o n e n t i a l dependence of a d s o r p t i o n energy on c o v e r a g e .
o r r
log = k - l o g . C
i n h
+k
(21)
A s t i l l f u r t h e r i s o t h e r m ( e q u a t i o n 22) i s a t t r i
b u t e d t o Tempkin and assumes a l i n e a r dependence o f t h e
a d s o r p t i o n energy on f r a c t i o n a l coverage.
= I
l o g C i h + const
n

(22)
9.
HAUSLER
Corrosion
Inhibition
295
T h i s assumption i s s u p p o r t e d i f a p l o t o f vs
l o g C ^ ^ yields a straight line.
I n t h i s c a s e , as i n
the case o f t h e F r e u n d l i c h i s o t h e r m , c o m p e t i t i v e ad
s o r p t i o n between i n h i b i t o r m o l e c u l e s and e i t h e r water
o r o t h e r c o n s t i t u e n t s o f t h e c o r r o s i v e medium i s p a r t
o f t h e assumptions.
Thus, except i n t h e case o f t h e
Langmuir i s o t h e r m , c o m p e t i t i v e a d s o r p t i o n i s r e c o g n i z e d
as i m p o r t a n t , hence t h e Langmuir i s o t h e r m seems some
what i d e a l , n o t w i t h s t a n d i n g t h e f a c t d i s c u s s e d e a r
l i e r , t h a t t h e a d s o r p t i o n may be h i g h l y s e l e c t i v e w i t h
r e s p e c t t o t h e e l e c t r o d e r e a c t i o n and may f u r t h e r m o r e
be p o t e n t i a l dependent.
Hence, i s o t h e r m p l o t t i n g i s
a t b e s t o n l y a means t o c o r r e l a t e d a t a and t o r e g i s t e r
p o s s i b l e c h e m i c a l e f f e c t s o f t h e system on a p u r e l y
comparative b a s i s . F o r a more d e t a i l e d d i s c u s s i o n o f
a d s o r p t i o n i s o t h e r m s i n e l e c t r o l y t e systems, t h e r e a d e r
i s r e f e r r e d to the
Parsons (26) Delaha
In t h e c o u r s e o f s t u d y i n g some a c e t y l e n i c i n
h i b i t o r s i n h y d r o c h l o r i c a c i d , a number o f d i f f e r e n t
i s o t h e r m type c o r r e l a t i o n were found.
Thus Fig.10
shows a Langmuir p l o t f o r 2 - b u t y n e - l , 4 - d i o l
i n 6N
h y d r o c h l o r i c a c i d under a e r a t e d c o n d i t i o n s . Two d i f
f e r e n t commercial p r o d u c t s o f t h i s compound were used.
I t i s shown t h a t t h e s t r a i g h t l i n e r e l a t i o n s h i p i s
o b t a i n e d w i t h a good r e p r o d u c i b i l i t y over t h r e e o r d e r s
o f magnitude o f i n h i b i t o r c o n c e n t r a t i o n .
In the l i g h t
o f what was s a i d above, t h i s was a s u r p r i s i n g r e s u l t ,
however, i t corresponds t o o t h e r s i m i l a r o b s e r v a t i o n s
reported i n the l i t e r a t u r e .
F i g . 1 1 .shows t h e same type o f p l o t f o r t h e i d e n t
i c a l i n h i b i t o r i n h y d r o c h l o r i c a c i d o f d i f f e r e n t con
centrations.
I t can now be seen t h a t i n weaker h y d r o
c h l o r i c a c i d the l i n e a r r e l a t i o n s h i p i s not r e t a i n e d .
At t h e h i g h e r i n h i b i t o r c o n c e n t r a t i o n s i n h i b i t i o n i s
reduced w i t h r e s p e c t t o 6N h y d r o c h l o r i c a c i d , w h i l e a t
the lower c o n c e n t r a t i o n s t h e i n h i b i t o r seems t o be
more e f f e c t i v e i n 4N than i n 6N h y d r o c h l o r i c a c i d .
The
decrease of i n h i b i t o r e f f i c i e n c y with decreasing a c i d
c o n c e n t r a t i o n i s unexpected.
No s i m i l a r r e s u l t s seem
t o have been r e p o r t e d e l s e w h e r e .
An i n t e r e s t i n g e f f e c t i s o b s e r v e d , F i g , 1 2 , when
the s i x normal h y d r o c h l o r i c a c i d s o l u t i o n i s d e a e r a t e d
with nitrogen.
I t i s seen t h a t t h e absence o f oxygen
reduces the e f f i c i e n c y o f the i n h i b i t o r c o n s i d e r a b l y .
F i n a l l y F i g . 13, shows a comparison o f 2 - b u t y n e - l ,
4 - d i o l , i n M-N h y d r o c h l o r i c a c i d under a e r a t e d and dea e r a t e d c o n d i t i o n s . While a t lower c o n c e n t r a t i o n s t h e
p r e s e n c e o f oxygen does n o t seem t o be i m p o r t a n t a t
higher concentrations better i n h i b i t o r e f f i c i e n c y i s

CORROSION CHEMISTRY
296
100
INHIBITOR CONCENTRATION (%)

Figure 10.
Inhibition of iron corrosion by 2-butyne-l,4-diol
in 6N H CI aerated

HAUSLER
Corrosion
Inhibition

Inhibitor Concentration (wt %)

Figure 12.
Inhibition of iron corrosion by 2-butyne-l,4-diol
in 6N HCl

9.
HAUSLER
Corrosion
Inhibition
299
100
INHIBITOR CONCENTRATION (wt %)

Figure 13.
Inhibition of iron corrosion by
2-butyne-l,4-diol

300
CORROSION
CHEMISTRY
observed i n d e a e r a t e d vs a e r a t e d h y d r o c h l o r i c a c i d , o r
i n o t h e r words, the r e v e r s e o f the e f f e c t observed i n
6N h y d r o c h l o r i c a c i d .
S i m i l a r experiments w i t h p r o p a r g y l a l c o h o l are
shown i n F i g . 1 4 .
T h i s s e r i e s o f experiments was
c a r r i e d out i n 4N h y d r o c h l o r i c a c i d under a e r a t e d and
d e a e r a t e d c o n d i t i o n s . A p p a r e n t l y a d i f f e r e n t mechanism
a p p l i e s f o r p r o p a r g y l a l c o h o l because the c u r v a t u r e of
the r e l a t i o n s h i p between p r o t e c t i o n and i n h i b i t o r conc e n t r a t i o n p l o t t e d i n Langmuir type f a s h i o n i s r e v e r s e d
from what was observed f o r b u t y n e - d i o l .
While the oxygen e f f e c t w i t h b u t y n e - d i o l i n 4N h y d r o c h l o r i c a c i d
was s i g n i f i c a n t o n l y a t h i g h e r i n h i b i t o r c o n c e n t r a t i o n s , i t becomes e v i d e n t t h a t f o r p r o p a r g y l a l c o h o l
oxygen r e d u c e s the i n h i b i t o r e f f i c i e n c y o v e r a l a r g e
c o n c e n t r a t i o n range.
Most i m p o r t a n t l y p r o p a r g y l
a l c o h o l i s more e f f e c t i v
In summary, i n d i r e c
d i c a t e some s u r p r i z i n g r e s u l t s .
F i r s t a rather large
e f f e c t o f s m a l l changes i n a c i d c o n c e n t r a t i o n i s obs e r v e d f o r the b u t y n e - d i o l .
I t would be r a t h e r d i f f i c u l t t o e x p l a i n t h i s i n terms o f a d s o r p t i o n t h e o r y
because the a d s o r p t i o n i s o t h e r m i n 4N h y d r o c h l o r i c
a c i d c r o s s e s the one o b t a i n e d i n 6N h y d r o c h l o r i c a c i d .
The pronounced and complex e f f e c t o f oxygen i s
even more unexpected i n terms o f a d s o r p t i o n t h e o r y ,
because oxygen i s not t h e r m o d y n a m i c a l l y s t a b l e under
the c o n d i t i o n s o f i r o n c o r r o s i o n i n h y d r o c h l o r i c a c i d .
Note a l s o , i n t h i s c o n t e x t , the oxygen e f f e c t i n 6N
h y d r o c h l o r i c a c i d i s e x a c t l y o p p o s i t e from 4N h y d r o chloric acid.
A n d , f i n a l l y , i n 4N a c i d we f i n d t h a t the
oxygen e f f e c t i s i n the same d i r e c t i o n f o r p r o p a r g y l
a l c o h o l and b u t y n e - d i o l , w i t h p r o p a r g y l a l c o h o l b e i n g
much s t r o n g e r a f f e c t e d . In terms o f a d s o r p t i o n t h e o r y
one would expect the b e t t e r i n h i b i t o r t o be adsorbed
more s t r o n g l y and hence l e s s a f f e c t e d by c o m p e t i t i v e
adsorption.
The e x p e r i m e n t a l r e s u l t s i n d i c a t e the
opposite.
A complete and e x t e n s i v e r a t i o n a l f o r the r e j e c t i o n o f a d s o r p t i o n t h e r o y i n the p r e s e n t case would
e a s i l y go beyond the frame work o f t h i s paper. Howe v e r , s i n c e i n the a r e a o f a c e t y l e n i c i n h i b i t o r s the
b u i l d - u p o f s u r f a c e f i l m s up t o 20 0 A has a l r e a d y been
o b s e r v e d (25), i t maybe more f r u i t f u l t o f o l l o w t h i s
l i n e of reasoning.
Further experimental e f f o r t , of
course, ought t o attempt t o c l a r i f y the n a t u r e o f t h i s
surface f i l m .
The above d e s c r i b e d e f f e c t s such as
the a c i d and the oxygen e f f e c t are not immediately
obv i o u s i f such a s u r f a c e f i l m i s o f the n a t u r e shown i n
T a b l e 6.
However, some o b s e r v a t i o n s i n v o l v i n g the de-

9.
HAUSLER
Corrosion
Inhibition
301
pendence o f i n h i b i t e d c o r r o s i o n r a t e s on f l o w r a t e may
shed f u r t h e r l i g h t on t h i s problem.
F i g . 1 5 , shows the c o r r o s i o n r a t e o f i r o n i n 4N
h y d r o c h l o r i c a c i d under a e r a t e d c o n d i t i o n s as a f u n c t i o n o f f l o w r a t e and d i f f e r e n t i n h i b i t o r c o n c e n t r a tions.
I t i s noted t h a t the b l a n k c o r r o s i o n r a t e i n c r e a s e s s l i g h t l y w i t h f l o w r a t e w h i l e a somewhat^
s t r o n g e r dependence i s o b s e r v e d f o r 0.01 and 0.02
per
cent i n h i b i t o r s o l u t i o n s . At the s t r o n g e r i n h i b i t o r
c o n c e n t r a t i o n (0.1%) the f l o w dependence becomes complex.
S i n c e t h e s e experiments were not c a r r i e d out under
i d e a l l y d e f i n e d f l o w c o n d i t i o n s the dependence o f c o r r o s i o n r a t e on f l o w r a t e w i l l be d i s c u s s e d o n l y i n a
q u a l i t a t i v e manner. Under l a m i n a r f l o w c o n d i t i o n s and
mass t r a n s f e r c o n t r o l one would have expected the c o r rosion rate to increas
v e l o c i t y w h i l e unde
a l i t y would p r e v a i l .
However, i n F i g . 1 5 one f i n d s t h a t
the c o r r o s i o n r a t e v a r i e s a p p r o x i m a t e l y w i t h the
0.2
t o 0.3 power o f the f l o w r a t e .
I t appears t h e r e f o r e
t h a t the o b s e r v e d dependence on the f l o w r a t e does not
obey c o n v e n t i o n a l mass t r a n s f e r t h e o r y .
A flow e f f e c t
might be e x p e c t e d i n u n i n h i b i t e d h y d r o c h l o r i c a c i d because hydrogen b u b b l e s , formed on the s u r f a c e o f t h e
m e t a l , are f a s t e r and more e a s i l y removed a t h i g h e r
flow r a t e s .
While t h i s argument c o u l d be a p p l i e d i n
d i s c u s s i n g F i g . 1 5 , we f i n d i n Fig.16 t h a t the f l o w
e f f e c t a t s i m i l a r c o r r o s i o n r a t e s i s much l e s s p r o nounced under d e a e r a t e d c o n d i t i o n s .
We t h e r e f o r e have
t o c o n c l u d e t h a t the o b s e r v e d f l o w e f f e c t i s not
mec h a n i c a l and cannot be r e l a t e d t o pure mass t r a n s f e r
c o n t r o l e i t h e r . In F i g . 1 7 , the f l o w dependence o f the
c o r r o s i o n r a t e i s shown f o r 2 - b u t y n e - l , 4 - d i o l i n dea e r a t e d 4N h y d r o c h l o r i c a c i d .
Note t h a t the c o r r o s i o n
r a t e appears t o be n o t i c e a b l y a f f e c t e d o n l y at t h e
higher flow r a t e s .
F i n a l l y , i n F i g . 1 8 , we observe t h a t
i n c r e a s e d f l o w r a t e can e i t h e r i n c r e a s e or d e c r e a s e the
c o r r o s i o n r a t e i n the p r e s e n c e o f an i n h i b i t o r .
This
e f f e c t was o b s e r v e d r e p r o d u c i b l y o n l y i n 6N h y d r o c h l o r i c a c i d w i t h 2 - b u t y n e - l , 4 - d i o l under d e a e r a t e d
c o n d i t i o n s f o r 0.2% and 0.1% i n h i b i t o r c o n c e n t r a t i o n .
T h i s b e h a v i o r i n d i c a t e s t h a t t h e c o r r o s i o n r a t e i s cont r o l l e d by the s u p e r p o s i t i o n o f two p a r t i a l r e a c t i o n
r a t e s each o f which i s mass t r a n s f e r dependent t o a
c e r t a i n extent.
In terms o f the model d e l i n e a t e d i n
T a b l e 6, i t i s suggested t h a t t h e
three-dimensional
p o l y m e r i c l a y e r made up by i n h i b i t o r m o l e c u l e s i s i n
fact a three-dimensional
c h e l a t e made up o f i r o n i o n s
and i n h i b i t o r m o l e c u l e s .
The c o r r o s i o n r a t e i s t h e n

150
4N HCI
100
50
10
Propargyl alcohol (deaerated)
Propargyl alcohol (aerated)
1,4-Butyne diol
(deaerated)
_
\
CL
I
0O00I
0.0005
0.001
0.005
CONCENTRATION
Figure 14.
0.05 0.1
0.01
(%)
Effectiveness of acetylenic inhibitors
1500
J 1000
<
or
0.01
%^vy-
500
c/)
^ ^ ^ - ^ C ) . 0 2
or
or
100
50
0.01
J7-
/ o
*^0J%
1
0.05
0.1
1
0.5
1
1.0
FLOWRATE (gal/min)
Figure 15.
Corrosion of iron in 4N HCI, propargyl alcohol aerated

9.
HAUSLER
Corrosion
Inhibition
303
1500
10
0.01
0.05
0.1
0.5
1.0
FLOWRATE (gal/min)
Figure 16.
Corrosion of iron in 4N H CI, propargyl alcohol deaerated

304
5000
FLOWRATE (gal/min)
Figure 17.
Corrosion of iron in 4N HCl, 2-butyne-l,4-diol
0.0
02
0.4
0.6
0.8
deaerated
1.0
FLOWRATE (gal/min)
Figure 18.
2-Butyne-l,4-diol,
0.2% ; (O) deaerated; () aerated

9.
HAUSLER
Corrosion
Inhibition
305
c o n t r o l l e d by the t h i c k n e s s of t h i s l a y e r which, i n t u r n ,
i s dependent on the f o r m a t i o n r a t e o f the c h e l a t e as
w e l l as i t s d i s s o l u t i o n r a t e . T h i s suggested model
i s n a t u r a l l y based on a number o f assumptions, such as
a p a r t i a l l y s o l u b l e c h e l a t e between the a c e t y l e n i c
i n h i b i t o r and i r o n , and a d i f f e r e n t c h e m i s t r y o f the
2 - v a l e n t from the 3 - v a l e n t c h e l a t e , i n o r d e r t o e x p l a i n
the oxygen e f f e c t .
S i n c e t h i s c h e l a t e has a f i n i t e
s o l u b i l i t y and i s c o n s t a n t l y formed d u r i n g the c o r r o s i o n p r o c e s s , one can u n d e r s t a n d t h a t i n one i n s t a n c e
i t s d i s s o l u t i o n r a t e i s r a t e d e t e r m i n i n g , w h i l e i n the
o t h e r i n s t a n c e i t s f o r m a t i o n r a t e maybe r a t e d e t e r m i n i n g , the l a t t e r b e i n g c o n t r o l l e d by the mass t r a n s f e r
of the i n h i b i t o r from t h e b u l k of the s o l u t i o n t o the
s u r f a c e of the m e t a l .
While many q u e s t i o n s i n t h i s
model have t o be l e f t open at t h i s stage and await
further investigation
an i n h i b i t e d i r o n e l e c t r o d
the n a t u r e o f the s u r f a c e c o r r o s i o n p r o d u c t l a y e r and
hence the i n t e r p h a s e c h e m i s t r y d e f i n e d above.
Fig.19
shows t y p i c a l p o l a r i z a t i o n curves o b t a i n e d i n 4N h y d r o c h l o r i c a c i d under a e r a t e d and d e a e r a t e d c o n d i t i o n s and
w i t h 0.5% p r o p a r g y l a l c o h o l (2M).
The r e s u l t s i n d i c a t e the time dependence of t h e p o l a r i z a t i o n curves
as w e l l as the dependence on scan r a t e . The b l a n k
c o r r o s i o n r a t e s , which can be seen t o i n c r e a s e w i t h
t i m e , are an i n d i c a t i o n o f the p r o g r e s s i v e l y l a r g e r
surface area.
The a n o d i c T a f e l s l o p e s a r e q u i t e i n dependent o f scan r a t e w h i l e the c a t h o d i c T a f e l s l o p e s
appear t o i n c r e a s e s l i g h t l y w i t h f a s t e r scan r a t e s .
T h i s l a s t e f f e c t may be an i n d i c a t i o n o f a d s o r p t i o n o f
a small impurity
i n the e l e c t r o l y t e .
The i n h i b i t e d
c o r r o s i o n r a t e s d e c r e a s e w i t h time and become e s s e n t i a l l y c o n s t a n t a f t e r about two h o u r s .
These s l o p e s are
not dependent on scan r a t e or on c o r r o s i o n r a t e .
The
most i n t e r e s t i n g e f f e c t i s o b s e r v e d when the i n h i b i t e d
hydrochloric a c i d s o l u t i o n i s aerated:
the anodic
T a f e l s l o p e i n c r e a s e s w h i l e the c a t h o d i c T a f e l s l o p e
d e c r e a s e s d r a m a t i c a l l y . As would have been e x p e c t e d
from the r e s i s t a n c e probe measurement the c o r r o s i o n
r a t e i n the a e r a t e d i n h i b i t o r s o l u t i o n i n c r e a s e s .
These o b s e r v a t i o n s have been found t o be o f g e n e r a l
n a t u r e i n d i f f e r e n t h y d r o c h l o r i c a c i d as w e l l as v a r y ing propargyl alcohol concentrations.
While most o f
the o b s e r v e d e f f e c t s i n Fig.19 c o u l d be e x p l a i n e d i n
terms o f c o n v e n t i o n a l e l e c t r o c h e m i c a l k i n e t i c s , the
f a c t i s t h a t i n the p r e s e n c e of oxygen and p r o p a r g y l
a l c o h o l the c a t h o d i c curve shows a l i m i t i n g c u r r e n t beh a v i o r and i s r a t h e r d i f f i c u l t t o u n d e r s t a n d .
However,
i f one were t o assume an i r o n - i n h i b i t o r c h e l a t e f i l m

306
0.5% Propargyl Alcohol, Deaerated

Slow Scan Rate, 0.2 mV/sec
Fast Scan Rate, 2.0 mV/sec
?orr -350 mV vs. AgCI
S
10,000
<
s^co^"
2 9 0
^ ^ < <^Blank
^ 6 0 min Slow (I)
^ 150 min Fast (I)
180 min Slow (H)
/80 min Fast
Aerated, Slow
^ry^
120 min Slow
1,000
120 min Slow

100 _20 min Slow
80 min Fast
Inhibited
20 min Slow
10
Anodi
I
80
1
120
40
40
80
120
Polarization 77 (mV)
Universal Oil Products
Figure 19.
Corrosion of iron in 4N hydrocaloric acid, aerated and deaerated with

propargyl alcohol as inhibitor
Table V I
PROTECTIVE
COMPLEX
METAL
I
F e F e ^ + 2e
HYDRODYNAMIC
BOUNDARY LAYER
BULK
FLUID
,1
2H + 2e
D AC
Fe
Fe
c
Inh
X ' e
e
A C
Inh
r
F e
Inh
o
F e + Inh + +
{Felnh}

9.
HAUSLER
Corrosion
307
Inhibition
on the s u r f a c e o f the m e t a l , which i s more s o l u b l e i f

the i r o n i s i n the t h r e e v a l e n t r a t h e r than the two
v a l e n t s t a t e one, can r e a d i l y u n d e r s t a n d t h a t a c a t h o d i c c u r r e n t w i l l be p a s s i v a t i n g w h i l e a n o d i c c u r r e n t
w i l l p r o g r e s s i v e l y decrease i n h i b i t i o n .
There i s t h e r e f o r e a c e r t a i n amount o f e v i d e n c e
i n d i c a t i n g the b u i l d up o f a d i s c r e t e phase on the
s u r f a c e o f the m e t a l c o n s i s t i n g most l i k e l y o f a
metal i n h i b i t o r - c h e l a t e s t r u c t u r e .
In o r d e r to f u r t h e r r a t i o n a l i z e the model, T a b l e 7 i n d i c a t e s the d i f f e r e n t p r o c e s s e s and parameters which c o n t r o l the
chemistry i n t h i s interphase.
The i r o n o x i d a t i o n
t a k e s p l a c e a t the i n t e r f a c e o f the
metal-chelate
l a y e r ( p r o t e c t i v e complex).
This then r e q u i r e s metal
i o n s t o m i g r a t e through the c h e l a t e l a y e r . The mechanism which p e r m i t s t h i s p r o c e s s t o t a k e p l a c e i s
borrowed from s e m i c o n d u c t i v
the e x i s t e n c e o f i r o
i o n s i n the c h e l a t e l a y e r .
Simultaneously, e l e c t r o n
h o l e s o r f r e e e l e c t r o n s have t o be p r e s e n t t o p r e s e r v e
the e l e c t r o n e u t r a l i t y . The c a t h o d i c r e a c t i o n may take
p l a c e a t the c h e l a t e - l a y e r / h y d r o d y n a m i c - b o u n d a r y l a y e r
i n t e r f a c e , o r a t the m e t a l s u r f a c e .
F u r t h e r m o r e , at
at the c h e l a t e l a y e r / h y d r o d y n a m i c - b o u n d a r y l a y e r i n t e r f a c e i r o n i o n s r e a c t w i t h the i n h i b i t o r t o form the
chelate.
I t i s f u r t h e r assumed t h a t the t h i c k n e s s o f
the c h e l a t e l a y e r i s r a t e c o n t r o l l i n g w i t h r e s p e c t t o
m i g r a t i o n o f charges t h r o u g h i t . The t h i c k n e s s i n
t u r n i s d e t e r m i n e d by the i r o n i o n c o n c e n t r a t i o n and
the i n h i b i t o r c o n c e n t r a t i o n g r a d i e n t t h r o u g h the
hydrodynamic-boundary l a y e r . Thus one can r e a d i l y
u n d e r s t a n d , a t l e a s t q u a l i t a t i v e l y how a v e r y complex
s u p e r p o s i t i o n o f mass t r a n s f e r r a t e s i n the h y d r o dynamic-boundary l a y e r and charge t r a n s f e r r a t e s i n
the c h e l a t e l a y e r combine t o g e n e r a t e the above d i s cussed r e s u l t s . Taking furthermore i n t o c o n s i d e r a t i o n
t h a t the c h e m i s t r y o f the c h e l a t e l a y e r i s dependent
on the v a l e n c e s t a t e o f i r o n , one can u n d e r s t a n d the
e f f e c t o f oxygen. While a t t h i s s t a g e , t h i s model i s
perhaps o n l y a r a t i o n a l e f o r the above d i s c u s s e d
e f f e c t s , i t i s c o n s i d e r e d a more u s e f u l model t h a n the
o l d and a n t i q u a t e d a d s o r p t i o n t h e o r i e s , l e a d i n g t o new
d i a g n o s t i c experiments.
Corrosion
fide
I n h i b i t i o n In The
P r e s e n c e Of Hydrogen S u l -
I n t r o d u c t i o n . The need f o r c o r r o s i o n p r o t e c t i o n
i n the p r e s e n c e o f hydrogen s u l f i d e a r i s e s most p r o m i n e n t l y i n the p e t r o l e u m i n d u s t r y , s p e c i f i c a l l y p r o -

308
CORROSION
CHEMISTRY
d u c t i o n o f crude o i l and t h e r e f i n i n g o f i t . The p r o cess streams i n t h e s e fundamental o p e r a t i o n s a r e

c h a r a c t e r i z e d i n t h a t t h e y c o n s i s t o f an aqueous and a
h y d r o c a r b o n phase i n v a r i o u s p r o p o r t i o n s . A l t h o u g h t h e
c o r r o s i o n i s caused by t h e aqueous phase and i t s cons t i t u e n t s , c o r r o s i o n i n h i b i t o r s used i n t h i s i n d u s t r y
are b o t h water and h y d r o c a r b o n s o l u b l e .
It i s intere s t i n g t o note t h a t t h e h y d r o c a r b o n s o l u b l e c o r r o s i o n
i n h i b i t o r s have i n t h e p a s t g i v e n t h e b e s t r e s u l t s and
t h e i r use i s s t i l l predominant, a r e c e n t NACE s u r v e y
not w i t h s t a n d i n g .
The importance o f t h e use o f c o r r o s i o n i n h i b i t o r s
i n t h e p e t r o l e u m i n d u s t r y as a whole can be gauged by
r e c e n t l i t e r a t u r e and p a t e n t r e v i e w s (29 .30 and u l )
There a r e b a s i c a l l y two t y p e s o f o i l s o l u b l e i n h i b i t o r s
which have p l a y e d a predominant r o l e
these are f a t t y
a c i d s and f a t t y amines
t h e voluminous p a t e n
r e a s o n s , no d i s t i n c t i o n i s made w i t h r e s p e c t t o t h e
s p e c i f i c use o f t h e s e two c l a s s e s o f i n h i b i t o r s .
N e v e r t h e l e s s , one f i n d s t h a t t h e f a t t y amines a r e p r e d o m i n a n t l y used i n hydrogen s u l f i d e c o n t a i n i n g media
w h i l e t h e f a t t y a c i d s have found a p p l i c a t i o n as c o r r o s i o n i n h i b i t o r s i n media c o n t a i n i n g oxygen and c a r bon d i o x i d e b u t no hydrogen s u l f i d e .
Since the r e a l i t y
of i n d u s t r i a l systems h a r d l y e v e r f i t s such neat c l a s s i fications,
i t i s not s u r p r i z i n g t h a t commercial i n h i b i t o r s a r e o f t e n m i x t u r e s o r s a l t s o f f a t t y amines
and f a t t y a c i d s , and t h a t c l a i m s o f s y n e r g i s m a r e o f t e n
found.
Both f a t t y amines and f a t t y a c i d s a r e known t o be
s u r f a c e a c t i v e , t h a t i s ' they adsorb on m e t a l s u r f a c e s
t h e r e b y f o r m i n g ahydrophobous f i l m which forms a water
impenetrable b a r r i e r .
Keeping water m o l e c u l e s away
from t h e m e t a l i n t e r p h a s e by a t h i n f i l m o f f a t t y
amines would reduce t h e o x y d a t i o n o f t h e m e t a l .
This
s i m p l e mechanism has l e a d t o t h e term " f i l m i n g amines"
as a g e n e r i c d e s c r i p t o r f o r t h i s group o f c o r r o s i o n
inhibitors.
The e x p e r i m e n t a l e v i d e n c e f o r t h i s s i m p l e
concept can be seen i n t h e p r a c t i c e o f p e r i o d i c i n h i b i t o r a p p l i c a t i o n r e s u l t i n g i n good c o r r o s i o n i n h i b i t i o n over extended p e r i o d s o f time.
For instance,
i n t h e o i l f i e l d , b e t t e r r e s u l t s a r e o b t a i n e d by t r e a t i n g s u b s u r f a c e equipment such as i n s e r t pumps, o i l w e l l
t u b i n g and s u c k e r rods p e r i o d i c a l l y w i t h a c e r t a i n
q u a n t i t y o f " f i l m i n g amine" i n h i b i t o r , r a t h e r than u s i n g such compounds on a c o n t i n u o u s b a s i s .
Many s t u d i e s
have been p u b l i s h e d d e t a i l i n g t h e f r e q u e n c y o f t h e
t r e a t m e n t as w e l l as t h e q u a n t i t y o f i n h i b i t o r used
p e r t r e a t m e n t as a f u n c t i o n o f o i l w e l l parameters (32

9.
HAUSLER
Corrosion
309
Inhibition
and H ) .
However, i f one l o o k s a t a s u b s u r f a c e s t r u c t u r e which was p u l l e d from an o i l w e l l , one f i n d s t h a t
the s u r f a c e i s not o n l y h y d r o p h o b i c but l o o k s b l a c k i n s t e a d o f m e t a l l i c , as one might expect from l a b o r a t o r y
experiments.
T h i s has s u b s e q u e n t l y
l e d t o the i d e a
t h a t the " f i l m i n g amine" i n h i b i t o r i s not adsorbed on
the m e t a l s u r f a c e but on an i r o n s u l f i d e f i l m c o v e r i n g
the m e t a l s u r f a c e .
While the r e s u l t o f a h y d r o p h o b i c
s u r f a c e i s the same, the l a t t e r concept l e a d s t o a
more r i g o r o u s d i s c u s s i o n o f the i n h i b i t i o n mechanism
and a v o i d s some o f the c o n f u s i o n which has been gene r a t e d by d i a g n o s t i c t e s t s which were based on s u r f a c e
a c t i v i t y o r w e t t i n g a n g l e measurements performed on a
c l e a n metal s u r f a c e .
The p r o o f o f the importance o f i r o n s u l f i d e i n
the i n t e r a c t i o n between the c o r r o s i o n i n h i b i t o r and
the m e t a l s u r f a c e wa
shown (lu)
that corrosio
enhanced and p r o l o n g e d when the c o r r o s i o n i n h i b i t o r
was adsorbed on a p r e s u l f i d e d specimen r a t h e r than on
the n o n s u l f i d e d s u r f a c e .
These measurements were made
e l e c t r o c h e m i c a l l y and gave s u p p o r t t o the p r a c t i c a l
well-known f a c t t h a t p e r i o d i c " f i l m i n g " c o u l d i n h i b i t
the c o r r o s i o n f o r r e l a t i v e l y l o n g p e r i o d s o f time.
In o r d e r t o u n d e r s t a n d the i r o n s u l f i d e - i n h i b i t o r
i n t e r a c t i o n , i t w i l l be n e c e s s a r y t o r e v i e w b r i e f l y
the c o r r o s i o n mechanism o f i r o n i n the p r e s e n c e o f
hydrogen s u l f i d e i n a two-phase medium.
C o r r o s i o n Of
I r o n In The
Presence Of Hydrogen S u l f i d e
I t has been known f o r a l o n g time t h a t i r o n

c o r r o d i n g i n the p r e s e n c e o f hydrogen s u l f i d e w i l l be
c o v e r e d by an i r o n s u l f i d e f i l m .
One would t h e r e f o r e have e x p e c t e d t h a t t h i s f i l m somehow a f f e c t s the
k i n e t i c s o f the c o r r o s i o n p r o c e s s .
S a r d i s c o and coworkers (35) c a r r i e d out c l a s s i c a l i n v e s t i g a t i o n s o f
the c o r r o s i o n k i n e t i c s o f i r o n as a f u n c t i o n o f the
p a r t i a l p r e s s u r e of hydrogen s u l f i d e and carbon d i oxide.
The a u t h o r s measured the o v e r a l l k i n e t i c s of
the c o r r o s i o n as w e l l as the r a t e of i r o n s u l f i d e f i l m
f o r m a t i o n and came t o some c o n c l u s i o n s w i t h r e s p e c t t o
the p r o t e c t i v e n e s s o f the i r o n s u l f i d e f i l m .
The r e s u l t s , however , were r a t h e r c o n f u s i n g and c o u l d not be
f i t t e d i n t o conventional r a t e theory.
I f i n f a c t the i r o n s u l f i d e b u i l d i n g up on the
s u r f a c e of the m e t a l r e p r e s e n t s a r e s i s t a n c e t o the
c o r r o s i o n p r o c e s s e s , t h e n one would expect t h a t the
c o r r o s i o n r a t e d e c r e a s e s as the i r o n s u l f i d e f i l m i n creases.
In o t h e r words the c o r r o s i o n k i n e t i c s would

310
not be l i n e a r ( c o n s t a n t c o r r o s i o n r a t e ) but p a r a b o l i c
( l i n e a r i t y between the c o r r o s i o n r a t e and the square
root of time).
I t was shown, however, t h a t the p a r a b o l i c i t y o f
s u l f i d e c o r r o s i o n i s e x t r e m e l y s e n s i t i v e t o the p r e sence o f minute q u a n t i t i e s o f oxygen.
It i s believed
t h a t many o f the e a r l i e r r e s u l t s may have been a f f e c t e d
by the i n c o m p l e t e e l i m i n a t i o n o f a i r from the c o r r o s i v e medium o r i t s i n a d v e r t e n t p r e s e n c e .
C a r e f u l measurements o f the c o r r o s i o n r a t e i n the
p r e s e n c e o f hydrogen s u l f i d e under r i g o r o u s e x c l u s i o n
o f a i r showed almost p e r f e c t p a r a b o l i c c o r r o s i o n k i n e t i c s , i n d i c a t i n g the r a t e c o n t r o l l i n g f a c t o r o f an
iron sulfide film (30.
I t was s u b s e q u e n t l y a l s o shown
i n (37) t h a t minute q u a n t i t i e s o f oxygen, as l i t t l e as
400 ppm i n the gas phase i n e q u i l i b r i u m w i t h the c o r r o s i v e media, a c c e l e r a t
10 times r e s u l t i n g i
kinetics.
F u r t h e r s t u d i e s (38) i n d i c a t e d t h a t the
t h i c k n e s s o f the r a t e c o n t r o l l i n g i r o n s u l f i d e f i l m
becomes c o n s t a n t a l t h o u g h the t o t a l i r o n s u l f i d e s c a l e
maybe much l a r g e r than t h a t .
T h i s was c o n f i r m e d by
e l e c t r o c h e m i c a l measurements o v e r l o n g p e r i o d s o f t i m e .
By a c t u a l l y w e i g h i n g the amount o f i r o n s u l f i d e b u i l t
up on the c o r r o d i n g specimen as a f u n c t i o n o f pH and
oxygen c o n c e n t r a t i o n (3JL)> i t was shown t h a t the "protectivness" o f the r a t e c o n t r o l l i n g i r o n s u l f i d e f i l m
i n c r e a s e s w i t h i n c r e a s i n g pH and d e c r e a s e s w i t h i n c r e a s i n g oxygen c o n c e n t r a t i o n .
However, the concent r a t i o n o f d i s s o l v e d s u l f i d i c s u l f u r has e s s e n t i a l l y
no e f f e c t on i r o n s u l f i d e f i l m i n the r e g i o n o f 1500
t o 25,000 ppm
(1Z).
A most s u r p r i s i n g b e h a v i o r was found when the pol a r i z a t i o n c u r r e n t o f a c o r r o d i n g specimen was o b s e r v e d
as a f u n c t i o n o f flow r a t e .
Fig.20
shows the r e s u l t s
which were o b t a i n e d .
A n o d i c and c a t h o d i c p o l a r i z a t i o n
c u r r e n t s i n m i l l i a m p s a t p o t e n t i a l s of +_ 50 m i l l i v o l t s
from the c o r r o s i o n p o t e n t i a l are p l o t t e d a g a i n s t f l o w
rate.
In s e v e r a l runs r e p r o d u c i b l e b e h a v i o r was
observed.
The c a t h o d i c c u r r e n t v a r i e s w i t h flow r a t e t o
the -g- t h power, w h i l e the a n o d i c c u r r e n t v a r i e s w i t h
f l o w r a t e t o the ^_ t h power. T h i s r e l a t i o n s h i p h o l d s
t r u e o v e r more t h a n one decade o f f l o w r a t e s .
It is
v e r y d i f f i c u l t t o e x p l a i n such r e s u l t s i n terms o f
c o n v e n t i o n a l mass t r a n s f e r l i m i t a t i o n s . I t i s w e l l
known t h a t the d i f f u s i o n l i m i t e d c u r r e n t v a r i e s app r o x i m a t e l y p r o p o r t i o n a l l y t o the f l o w r a t e i n the t u r b u l e n t r e g i o n and w i t h the square r o o t o f f l o w r a t e i n
the l a m i n a r r e g i o n .
I f on the o t h e r hand the p o l a r i z a t i o n c u r r e n t was t r a n s p o r t l i m i t e d a c r o s s the c o r r o s i o n

HAUSLER
Corrosion
Inhibition
Polarization Current at - E
C Q | T
= 5 0 mV
2nd Run
1st Run
2nd Run
Anodic
0.05
J ~V
0.1
0.2
0.4
0.6 0.8 1.0
FLOWRATE (gal/min)
Figure 20.
Iron corroding in H S containing medium

2
Table VIII
METAL
LIQUID
SCALE
Corrosion: Fe Fe + 2e
H S - FeJ + 2 + FeS + H
2
2H = H + 2
+
{H S + 1/2 0 = H 0 + S + 2}
=
2e + 2 -
Fe + FeJ -
++
Solid State Transfer

a(Fep)
~~dx
d()
dx
Liquid Tronsfer
dC +
ti
D +
u
"
s

312
CORROSION
CHEMISTRY
p r o d u c t l a y e r , n o dependency on f l o w r a t e s h o u l d be
found.
I t i s t h e r e f o r e n e c e s s a r y t o p o s t u l a t e a more com
p l e x mechanism, such as i s suggested i n T a b l e 8.
Since
the c o r r o d i n g m e t a l i s covered by a c o r r o s i o n p r o d u c t
l a y e r , the f o l l o w i n g r e a c t i o n s have t o t a k e p l a c e a t
the m e t a l / s c a l e i n t e r f a c e : a. o x i d a t i o n o f i r o n ; b. the
consumption o f e l e c t r o n h o l e s by e l e c t r o n s ( o r p o s s i b l y
d i s c h a r g e o f p r o t o n s w i t h subsequent s o l u t i o n o f h y d r o
gen i n the m e t a l ) ; c. the combinatio n o f i r o n i o n v a
c a n c i e s w i t h newly formed i r o n i o n s . The l a t t e r two
p r o c e s s e s take p l a c e w i t h the r e l e a s e o f energy.
These
r e a c t i o n s n e c e s s i t a t e a c o n c e n t r a t i o n g r a d i e n t through
the c o r r o s i o n p r o d u c t l a y e r o f i r o n i o n v a c a n c i e s and
electron holes.
( I t i s u n d e r s t o o d t h a t the mechanism
c o u l d be w r i t t e n i n terms o f i r o n i o n s moving i n t e r s t i t i a l l y , i n which
t r o n conductor.
Thi
ever).
S i n c e the c o r r o s i o n p r o c e s s t a k e s p l a c e w i t h
f o r m a t i o n o f i r o n s u l f i d e the f o l l o w i n g r e a c t i o n s have
t o take p l a c e a t the s c a l e l i q u i d i n t e r f a c e : a. f o r
mation o f i r o n s u l f i d e and i r o n i o n v a c a n c i e s ; b. d i s
charge of p r o t o n s t o form hydrogen and e l e c t r o n h o l e s ;
c. i f oxygen i s p r e s e n t , the e l e c t r o n h o l e s can be
formed by r e d u c t i o n o f oxygen. The f o r m a t i o n o f hy
drogen from p r o t o n s a l s o n e c e s s i t a t e s a p r o t o n con
c e n t r a t i o n g r a d i e n t i n the l i q u i d phase ( i f oxygen i s
p r e s e n t , the c o r r e s p o n d i n g oxygen c o n c e n t r a t i o n g r a d
i e n t would have t o e x i s t as w e l l ) .
The r e a c t i o n s t a k
i n g p l a c e a t the s c a l e l i q u i d i n t e r p h a s e can be v i s
u a l i z e d as e q u i l i b r i u m r e a c t i o n s . T h i s means t h a t the
s u l f i d e c o n c e n t r a t i o n i n f l u e n c e s the i r o n i o n vacancy
c o n c e n t r a t i o n i n the s c a l e , and the p r o t o n concen
t r a t i o n i n the l i q u i d a f f e c t s the e l e c t r o n h o l e con
c e n t r a t i o n i n the s c a l e .
S i n c e the n a t u r e of the
s c a l e determines the r a t e o f the s o l i d s t a t e t r a n s f e r
phenomena, and the f l o w r a t e determines the l i q u i d
boundary l a y e r c o n c e n t r a t i o n g r a d i e n t , hence the
l i q u i d - s o l i d i n t e r f a c i a l p r o t o n , H S and oxygen concen
t r a t i o n s , i t f o l l o w s t h a t l i q u i d and s o l i d s t a t e mass
and charge t r a n s f e r a r e l i n k e d t o g e t h e r by the c h e m i c a l
e q u i l i b r i a e s t a b l i s h e d a t the s c a l e - l i q u i d i n t e r f a c e .
An attempt was made t o f o r m u l a t e t h e s e r e l a t i o n
s h i p s a n a l y t i c a l l y , i n o r d e r t o c o n f i r m the dependence
o f c o r r o s i o n r a t e on f l o w r a t e observed i n F i g . 2 0 .
Thus e q u a t i o n 23 r e s t a t e s the f o r m a t i o n o f i r o n i o n
v a c a n c i e s and e l e c t r o n h o l e s a t the s c a l e / l i q u i d i n t e r
face.
HS
l-*Fe + 2 + FeS + H
(23)
2

9.
HAUSLER
Corrosion
313
Inhibition
2-**2H
2H+
2(FeS)
(24)
+ Fe"
= (H*) +
(25)
()
I t i s a l s o assumed, f o l l o w i n g Simkovich (2JL), t h a t

p r o t o n s can d i s s o l v e i n t e r s t i t i a l l y i n the i r o n s u l f i d e
l a t t i c e ( e q u a t i o n 24).
The r e q u i r e m e n t f o r e l e c t r o n e u t r a l i t y i n the i r o n s u l f i d e l a t t i c e l e a d s t o e q u a t i o n
25.
Assuming the r a t i o o f hydrogen p a r t i a l p r e s s u r e t o
h y d r o g e n s u l f i d e p a r t i a l p r e s s u r e t o be c o n s t a n t ,
e q u a t i o n s 2 3 through 2 5 can be r e a r r a n g e d t o :
2
Kr
(H+)
(26)
()*
and
(27)
()'
A +
(H )
i n d i c a t i n g t h e cube o f t h e e l e c t r o n h o l e c o n c e n t a t i o n
t o be i n v e r s e l y p r o p o r t i o n a l t o t h e p r o t o n c o n c e n
tration.
A c c o r d i n g t o B e n n e t t and Meyers (40.) t h e mass
f l u x a c c r o s s t h e l i q u i d boundary l a y e r can be f o r m u l a t
ed as f o l l o w s :
1/3
Re}- (Sc)
K"3 ( CH
N
H+
cath
(28)
= K
(C^+-C +) (Urn) *
0
H +
c )
where (%+-C +) = P r o t o n g r a d i e n t i n l i q u i d boundary

layer
Re^
= Reynolds number
Sc
= S c h m i t t number
Urn
= Average f l o w v e l o c i t y
K4
= combined c o n s t a n t s
S i n c e i n the system i n v e s t i g a t e d o n l y the l i n e a r
v e l o c i t y changes, a l l o t h e r v a r i a b l e s and c o n s t a n t s are
lumped t o g e t h e r i n
. Assuming now t h a t the e l e c
t r o n i c c o n d u c t i v i t y o f the s c a l e i s the l i m i t i n g f a c
t o r r a t h e r than the i o n i c one, the c a t h o d i c c u r r e n t can
be s e t t o be p r o p o r t i o n a l t o the e l e c t r o n h o l e concen
t r a t i o n times the e l e c t r o n h o l e m o b i l i t y :
H
(29)
cath
S u b s t i t u t i n g e q u a t i o n 27
into equation
29

314
( i
and
cath
catn
) 3
=*
:
A+B(H )
f i n a l l y with equation
(i
)3 cath
"
Q l
28
K
cu
U
1/2
m
"
4
t a
o^2 ^" ^
n s
(31)
B
icath
I t i s d i f f i c u l t t o estimate a l l the constants i n

q u a t i o n 31 i n o r d e r t o a r r i v e a t a q u a n t i t a t i v e e v a l u a tion.
However, s i n c e t h e c u r r e n t i n c r e a s e s w i t h i n c r e a s i n g mean v e l o c i t y , i t might be s a i d t h e e f f e c t s
n e a r l y c a n c e l i n t h e denominator o f e q u a t i o n 3 1 . T h i s
would mean t h a t i n d e e d t h e c a t h o d i c c u r r e n t becomes a l most p r o p o r t i o n a l t t h
velocit
w i t h t h 1/6
power. Even though
quantitative, i t s t i l
suggests a reasonable e x p l a n t i o
f o r t h e r a t h e r u n u s u a l mass t r a n s f e r e f f e c t o b s e r v e d
i n F i g . 20.
The above r a t i o n a l e a p p l i e s o n l y t o t h e
c a t h o d i c c u r r e n t , however, a s i m i l a r d e r i v a t i o n can be
used t o c a l c u l a t e t h e a n o d i c c u r r e n t dependence on
flow r a t e .
I n h i b i t o r I n t e r a c t i o n With The I r o n S u l f i d e S u r f a c e
Since protons are discharged i n the c o r r o s i o n process,
and s i n c e t h e s e p r o t o n s a r e f u r n i s h e d from t h e c o r r o s i v e medium, t h e r e must e x i s t some mechanism f o r p r o t o n a d s o r p t i o n on t h e i r o n s u l f i d e s u r f a c e .
It is
r e a s o n a b l e t o assume t h a t on t h e i r o n s u l f i d e s u r f a c e
t h e r e a r e s u l f i d e g r o u p s , t h e v a l e n c e s o f which a r e
not t o t a l l y n e u t r a l i z e d by i r o n m o l e c u l e s .
These
p a r t i a l l y n e u t r a l i z e d s u l f i d e c e n t e r s can adsorb p r o tons.
This leads to the p o s t u l a t i o n of a protonated
i r o n s u l f i d e s u r f a c e group:
- F e S H . This surface
group f a c i l i t a t e s t h e d i s c h a r g e o f hydrogen a c c o r d i n g
to equation 32.
2 JFeS - H ( - 2 z~*z2 JFe-S~| + H
(32)
where :
= e l e c t r o n h o l e ; p o s i t i v e charge
In o r d e r t o stop t h e c o r r o s i o n p r o c e s s t h i s r e
a c t i o n has t o be impeded.
T h i s can be a c h i e v e d i f t h e
p r o t o n adsorbed on t h e s u r f a c e c o n t a i n i n g t h e i r o n s u l
f i d e s p e c i e s i s r e p l a c e d by a c a t i o n , t h e r e d u c t i o n o f
which i s n o t as e a s i l y a c c o m p l i s h e d as t h e r e d u c t i o n
of t h e p r o t o n .
I t i s s u g g e s t e d t h a t t h e a l k y l ammonium

9.
HAUSLER
Corrosion
315
Inhibition
i o n can d i s p l a c e the p r o t o n v i a an i o n exchange mechanism d e s c r i b e d i n quation 3 3 , the e q u i l i b r i u m cons t a n t o f t h i s r e a c t i o n b e i n g d e s i g n a t e d as K^:

JFeS-Hf +
where :
>
FeS-RNH^f
RNH^
^=^5JFeS-RNH | + H
(33)
= surface
complex
I t s h o u l d be noted t h a t t h i s i s not a simple ads o r p t i o n o f the a l k y l ammonium i o n on the s u r f a c e of

the i r o n s u l f i d e but can be c o n s i d e r e d as an i o n i c r e a c t i o n i n which a p r o t o n i s b e i n g s e t f r e e . I t i s now
r e a s o n a b l e t o c o n s i d e r the f a c t o r s which may i n f l u e n c e
the c o n c e n t r a t i o n o f t h e s u r f a c e complex formed from
i r o n s u l f i d e and the a l k y l ammonium i o n
Going
t h r o u g h a simple s e r i e
i t i s found t h a t th
p l e x e q u a l s the p r o d u c t o f a s e r i e s o f e q u i l i b r i u m cons t a n t s times the p r o t o n c o n c e n t r a t i o n o f the medium, as
shown i n e q u a t i o n
34.
(JFeS-RNH |)
3
(H )
' C
(34)
where :
(H )
formation constant
d i s s o c i a t i o n constant of surface
d i s s o c i a t i o n c o n s t a n t o f amine
proton concentration
c o n c e n t r a t i o n of amine
c o n c e n t r a t i o n of s u r f a c e - s u l f i d e
JFe-S"|
FeS-H
JFe-SH|
The two main f a c t o r s which a f f e c t the concent r a t i o n o f the s u r f a c e complex are i t s f o r m a t i o n cons t a n t K4 and the pH.
The l a t t e r has been shown t o be
true experimentally (Table
9).
C h e m i s t r y Of C o r r o s i o n I n h i b i t o r s . There are two
q u e s t i o n s which a r i s e w i t h r e s p e c t t o
. These are
1. How can the f o r m a t i o n c o n s t a n t o f the s u r f a c e comp l e x be i n c r e a s e d ?
2. Why i s n ' t the a d s o r p t i o n p r o c e s s r e v e r s i b l e ?
That i s t o say, why do s m a l l c o n c e n t r a t i o n s o f amine
(0.25 ppm) l e a d t o l a r g e s u r f a c e coverage and consequently large i n h i b i t o r e f f i c i e n c y ?
A l t h o u g h water m o l e c u l e s do not appear i n Equat i o n 34, i t i s n e v e r t h e l e s s r e a s o n a b l e t o assume t h a t

316
T a b l e IX
Concentration
Inhibitor
Armand
i n ppm f o r 90-95% P r o t e c t i o n
pH
4.2-4. 5
2.5
pH
6-6.5
pH
7-7.2
10-15
20
10
20
3-4
7-10
20
P e t e r E.
0.2
n. a.
n. a.
Conny E.
0.25-0. 5
Teddy E.
0.2-0. 3
2-3
Kathy
2.5-3
Norman
Dora
Talbot
the i r o n s u l f i d e s u r f a c e i s c o v e r e d w i t h a l a y e r o r
more o f water m o l e c u l e s , because t h e p r o t o n adsorbed
on t h e .surface i r o n s u l f i d e has a tendency t o d i s s o c i a t e and, t h e r e f o r e , needs t o be s o l v a t e d .
The f r e e
a l k y l ammonium i o n and i t s c o u n t e r i o n , e.g.., a b i s u l f i d e i o n , a r e both s o l v a t e d by water.
In the adsorpt i o n s t e p an e l e c t r o n i c a l l y n e u t r a l s u r f a c e complex
i s formed. Thus, a p r o t o n s o l v a t e d by water and i t s
c o u n t e r i o n , t h e b i s u l f i d e i o n , a r e s e t f r e e . The
e s s e n t i a l l y n e u t r a l s u r f a c e complex, does n o t r e q u i r e
s o l v a t i o n and because o f i t s h y d r o p h o b i c n a t u r e w i l l
have a tendency t o d i s p l a c e water m o l e c u l e s from t h e
iron s u l f i d e surface.
Since the desorption process
would a g a i n r e q u i r e s o l v a t i o n o f t h e i r o n s u l f i d e s u r f a c e , i t can no l o n g e r t a k e p l a c e because water molec u l e s a r e permanently d i s p l a c e d from t h e s u r f a c e by
the h y d r o p h o b i c n a t u r e o f t h e s u r f a c e complex. As a
consequence i t can be p r e d i c t e d t h a t an i n h i b i t o r w i t h
a h i g h e r l i p o p h i l i c c h a r a c t e r w i l l be more permanently
adsorbed.
I t i s known t h a t amines become more l i p o p h i l i c ,
or water i n s o l u b l e , w i t h i n c r e a s i n g a l k y l c h a i n l e n g t h .
Thus water s o l u b l e amines such as m o r p h o l i n e ( T a b l e l O )
show no i n h i b i t i o n e f f i c i e n c y a t t h e s e s m a l l concent r a t i o n s because t h e i r a d s o r p t i o n i s as easy as t h e i r
desorption.


Cll
Alkyl_
0
0
5
10
0
81
97
0.5
2
5
30
100
0.5
1
56
97
99
100
0.125
0.25
0.5
0.75
Morpholine
Concen P r o t e c
tion
tration
%
ppm
ft/sec
0.062
Propylenediamine
Concen P r o t e c
tion
tration
%
ppm
HS
Protec
tion
%
1 5
C
Alkyl^
Propylenediamine
Concen P r o t e c
tion
tration
%
ppm
Toluene-Water, S a t u r a t e d w i t h
2 00 ppm C I "
70C
Carbon S t e e l , l i n e a r v e l o c i t y
Concen
tration
ppm
Tallow
Propylenediamine
Conditions :
E f f e c t i v e n e s s of Various A l k y l Propylenediamines
and
Water S o l u b l e Amines as P r o c e s s C o r r o s i o n I n h i b i t o r s
CO
h-*
g-
cl
>
318
CORROSION CHEMISTRY
Table 10 also shows a comparison between differ

ent propylenediamine derivatives with decreasing mole
cular weight. A tallow propylenediamine (C^g) which
has been proposed as a process corrosion inhibitor in
the literature many times, is a very efficient materi
al.
As the molecular weight decreases due to a re
duction of the alkyl chain length to 15 C-atoms and
11 C-atoms the corrosion inhibiting tendency decreases
gradually. This would have been expected because the
water solubility of these compounds increases with de
creasing alkyl chain length.
Yet another way to vary the formation constant of
the surface complex is to change the number of amine
groups in the molecule. One of the f i r s t process
corrosion inhibitors proposed in the literature was
oleylamine. As has been shown in (2J.) oleylamine is
quite effective in
propylenediamine derivativ
molecular weight i s , however, at least ten times as
active as oleylamine.
This concept represents a new theory for the ac
tion of process corrosion inhibitors. In contrast to
the old filming amine theory the new one is based on
a specific adsorption mechanism involving an ion ex
change step. It can correctly predict the decrease of
protection efficiency with increasing pH. It also ex
plains structural differences between inhibitors such
as increased efficiency of propylenediamine deriva
tives over primary amines and decreased efficiency
with decreasing molecular weight of the amine group
compound.
Literature Cited
1. Annand, R.R., Hurd, R.M., Hackerman, N., J. Electrochem. Soc, 112, 138, (1965).
Parsons, R., 3rd European Symposium on Corr. Inhib.,
Ferrara, Italy, 1970, Proceedings p. 3 (1971).
2. Wagner, C., Traud, W., Z. Electrochemie 44 391
(1938).
3. Kaesche, ., Die Korrosion der Metalle, Springer
Verlag, Berlin 1966, p. 68.
4. Fischer, ., 3rd European Symposium on Corr. Inhib.,
Ferrara, Italy, 1970 Proceedings, p. 16(1971).
5. Nathan, C., Corrosion Inhibitors, National Associ
ation of Corrosion Engineers, Houston, Texas,
1973 , cf. Riggs, O.L. p. 7.
6. Vetter, ., Electrochemical Kinetics, Academic
Press, New York, London, 1967.

9. HAUSLER
Corrosion Inhibition
319
7. Hackerman, N., Corrosion/74, National Meeting of

the NACE, Chicago, 111., paper 73, (1974).
8. Nobe, ., Hussein, ., Corrosion/73, Annual Meet
ing NACE, paper #26 (1973).
9. Stern, M., J. Electrochem. Soc. 102 609 (1955).
10. Mansfeld, F., Corrosion, 32 (4) 143 (1976).
11. Hausler, R.,., Corrosion, 33 (4) 117 (1977).
12. Hoar, T.P., Holliday, R.D. J. Appl. Chem. 3 502
(1953).
13. Kaesche, ., Hackerman, N., J. Electrochem. Soc.
105, 4, (1958).
14. Elze, J., Fischer, H., J. Electrochem. Soc. 99,
259 (1952).
15. Kaesche, H., Z. Electrochemie 63, 492 (1959).
016. Hoar, T.P., Pittsburgh Intern. Conf. Surface Re
actions, p
lications Compan
17. Bartonicek, R., Proc. 3rd Internat'l Congr. on
Mettallic Corrosion, Moscow, 1966 Vol. 1
p. 119 (1969).
18. Kolotyrkin, Y.,., Trans. Faraday Soc. 55, 455
(1959).
19. Ross, T.K., Jones, D.H., J. Applied Chem. 12, 317
(1962).
20. Tedeschi, R., Proceedings of the 25th Conference,
NACE, March, 1969, p. 173, (1970).
21. Tedeschi, R., National Conference NACE, Annaheim
Calif. 1973, paper #24.
22. Tedeschi, R., Corrosion, 31 (4) 130, (1975).
23. Poling, G.W., J. Electrochem. Soc. Vol. 114, 1209
(1967).
24. Hausler, R.H., Corrosion, 33 (4) 119 (1977).
25. Gardner, G., Corrosion Inhibitors, C. Nathan
editor, National Assoc. Corrosion Engineers,
Houston, Texas (1973).
26. Parsons, R., Advances in Electrochemistry and
Electrochem. Eng. Vol. 1, ed. Delahay p. 65
Interscience, New York, (1961).
27. Delahay, P., Double Layer and Electrode Kinetics,
Wiley, New York, (1965).
28. Bockris, M., Modern Electrochemistry, Plenum Press
(1972).
29. Ranney, M.W., Corrosion Inhibitors, Manufacture
and Technology, Noyes Data Corporation, Park
Ridge, N.J. (1976).
30. Bregman, J.I., Corrosion Inhibitors, The Mac Millan
Co., New York, N.Y., p. 198 (1963).
31. Nathan, C., Corrosion Inhibitors, National Assoc.
Corr. Engineers, Houston, Texas, 1973 cf.p.42

320
CORROSION CHEMISTRY
32. L a r r i s o n , K.L., Use of P o l a r i z a t i o n Data In the

F i e l d Evaluation of Oil Well Corrosion Treatment, paper presented at the NACE South Central Region, Conference, Oct. 18, 1966.
33. Frank, W.J., The Oil and Gas Journal May 31, p. 63
(1976).
34. Hausler, R.H., Proceedings 3rd. European Symposium
Corr. I n h i b i t o r s , Ferrara, I t a l y , (19 70) p.399
(1971).
35. Sardisco, T.B., Corrosion 19 354 (1963), Corrosion
21 69 (1965).
36. Hausler, R.H., Materials Performance, 13, ( 9 ) ,
16 (1974).
37. Hausler, R.H., e t . a l . , Corrosion/74, Annual NACE
Meeting, Chicago, Ill., paper #123 (1974).
38. Hausler, R.H., NACE Annual Meeting Philadelphia
P.A., pape
39. Simkovich, G., e t . a l
Meeting API, Div. Refining, Chicago, Ill.
May 12, (1969).
40. Bennet, C.O., Meyers, J.E., Momentum, Heat and Mass
Transfer, McGraw Hill Publishing Co.,(1975).
RECEIVED September 1, 1978.

10
Stress-Corrosion Cracking
J. C. SCULLY
Department of Metallurgy, University of Leeds, Leeds LS2 9JT, England
S t r e s s c o r r o s i o n c r a c k i n g i s t h e phenomenon by
which
alloys
fail
by c r a c k i n g when s i m u l t a n e o u s l y
s t r e s s e d and expose
occur at stress l e v e l
cause
failure
in
air.
While the a p p l i c a t i o n o f the
s t r e s s may be
multi-axial,
it
is
n e c e s s a r y f o r it t o
have a
tensile
component and c r a c k i n g will u s u a l l y
occur p e r p e n d i c u l a r l y to
it.
Stress corrosion cracking
r e p r e s e n t s the most h i g h l y
localized
form o f c o r r o s i o n
t h a t is e v e r e n c o u n t e r e d .
W h i l e t h e d i s c u s s i o n in this c h a p t e r i s c o n f i n e d
to
metallic
alloys,
s t r e s s c o r r o s i o n c r a c k i n g is p a r t
o f a l a r g e r range o f phenomena, s i n c e s i m i l a r
failures
o c c u r in n o n m e t a l l i c m a t e r i a l s ,
e.g.,
g l a s s in H2O,
o r g a n i c polymers in p o l a r s o l v e n t s , a l u m i n a in H2O.
F u r t h e r m o r e , w h i l e most o f the d i s c u s s i o n is c o n f i n e d
t o a l l o y s c r a c k i n g in aqueous e n v i r o n m e n t s , s i m i l a r
c r a c k i n g in some alloys o c c u r s in o r g a n i c
liquids,
steam, d r y gases and in b o t h liquid and solid m e t a l s .
The amount o f c o r r o s i v e may be q u i t e s m a l l .
Failures
have been c a u s e d , f o r example, by t h e
perspiration
residue of a single
fingerprint.
Within the confines
o f a s h o r t c h a p t e r , it is n o t p o s s i b l e t o d i s c u s s
e v e r y example o f such
failures.
The d e s c r i p t i o n s b e low a r e c o n f i n e d m a i n l y t o s t r e s s c o r r o s i o n c r a c k i n g i n
aqueous m e d i a .
As an
industrial
problem s t r e s s c o r r o s i o n c r a c k i n g
is o f c o n s i d e r a b l e i m p o r t a n c e .
There is a l o n g h i s t o r y
o f major and minor
failures,
particularly
i n the c h e m i c a l i n d u s t r y and in t h e t r a n s p o r t i n d u s t r y ,
particularly
o f components i n s h i p s and p l a n e s . It is a major
potential
s o u r c e o f failure in t h e n u c l e a r power
i n d u s t r y in w h i c h , f o r example, a u s t e n i t i c s t a i n l e s s
s t e e l s may fail i n h i g h purity water c o n t a i n i n g oxygen
and c h l o r i d e i o n s a t t h e level o f p p b .
0-8412-0471-3/79/47-089-321$07.50/0

322
A l a r g e amount o f r e s e a r c h e f f o r t has been d e v o t e d

t o t h e s u b j e c t and t h e p u b l i s h e d l i t e r a t u r e i s q u i t e
immense. Many c o n f e r e n c e s have been h e l d . Anyone
c o n c e r n e d t o l e a r n more about t h e s u b j e c t can f i n d h i s
way by t a k i n g (1_/<2/3_/4 s)
as a s t a r t i n g p o i n t .
There comes a p o i n t w i t h most t e c h n o l o g i c a l p r o b lems when s u f f i c i e n t i s known about a s u b j e c t t o e n a b l e
p r e d i c t i o n s t o be made. These may be made p o s s i b l e by
a f u n d a m e n t a l u n d e r s t a n d i n g o f t h e p r o b l e m o r by t h e
development o f e m p i r i c a l r e l a t i o n s h i p s w h i c h have been
d i s c e r n e d w i t h o u t an a p r i o r i u n d e r s t a n d i n g .
To the
p r a c t i s i n g metal user
e i t h e r background i s a c c e p t a b l e
provided that i t gives s u f f i c i e n t p r e d i c t i v e capacity
w i t h w h i c h t o a v o i d o r a t l e a s t reduce t h e i n c i d e n c e o f
failures.
T h i s s t a g e has n o t been r e a c h e d w i t h s t r e s s
c o r r o s i o n c r a c k i n g . A l o t i s known about t h e p r o b l e m
but i t i s not alway
when o r even whethe
to show below why t h i s u n c e r t a i n t y e x i s t s . I t must a l s o
be added t h a t t h e method o f t e s t i n g becomes i m p o r t a n t .
This, too, i s therefore discussed.
I n t h i s c h a p t e r some g e n e r a l remarks a r e made
about t h e p r o b l e m . T h i s i s f o l l o w e d by a d e t a i l e d d i s c u s s i o n o f mechanisms, and a t t h e end p r e v e n t a t i v e
measures a r e i n d i c a t e d .
f
General Features
of Stress Corrosion
Cracking
Stress corrosion cracking i s a complicated subject,

u n l e s s t h a t i s emphasized a t t h e b e g i n n i n g , t h e n t h e
f i n e d e t a i l s o f p h e n o m e n o l o g i c a l and m e c h a n i s t i c f a c t o r s w i l l n o t be a p p r e c i a t e d .
I n o r d e r t o g a i n some
understanding of s t r e s s c o r r o s i o n c r a c k i n g , i t i s necessary to r e a l i z e t h a t three d i f f e r e n t d i s c i p l i n e s are at
work i n any s t r e s s c o r r o s i o n s i t u a t i o n . These a r e
p h y s i c a l m e t a l l u r g y , e l e c t r o c h e m i s t r y and f r a c t u r e
mechanics.
P h y s i c a l M e t a l l u r g y . A l l c o m m e r i c a l m e t a l comp o n e n t s a r e p o l y c r y s t a i l i n e and a l l m e t a l l a t t i c e s c o n t a i n b o t h p o i n t and l i n e f a u l t s .
Heat t r e a t a b l e a l l o y s
f r e q u e n t l y c o n t a i n p r e c i p i t a t e s w h i c h may be v e r y s m a l l
(< 5 pm d i a ) . A l l a l l o y s c o n t a i n major a l l o y i n g e l e ments b u t t h e y c o n t a i n a l s o a range o f n o n d e l i b e r a t e
e l e m e n t s , b o t h m e t a l l i c and n o n m e t a l l i c i n n a t u r e .
It
i s p o s s i b l e t o show t h a t a l l t h e s e f a c t o r s , as w e l l as
s u r f a c e f i n i s h , r e s i d u a l c o l d work and m e t a l l u r g i c a l
h i s t o r y (what was done t o t h e a l l o y i n b r i n g i n g t h e component t o i t s p r e s e n t shape) may have an e f f e c t on

10.
SCULLY
Stress-Corrosion
Cracking
323
stress corrosion cracking, making an a l l o y more suscept i b l e or l e s s . D i f f e r e n t batches of one a l l o y , both

meeting the same a l l o y s p e c i f i c a t i o n may e x h i b i t
markedly d i f f e r e n t l e v e l s of s u s c e p t i b i l i t y , which i s
merely to say that s p e c i f i c a t i o n s , embodying as they do
ranges of a l l o y i n g elements acceptable to the industry,
a r i s e usually from processing and manufacturing considerations, and not from stress corrosion considerations.
A lack of appreciation of such points, with which a
m e t a l l u r g i s t w i l l usually be conversant, can cause
much f r u s t r a t i o n and bewilderment to nonmetallurgists.
Grain s i z e i s of importance, an a l l o y generally becoming more susceptible as the s i z e i s increased.
Grain
shape i s also of importance. A f t e r a manufacturing
process during which grain growth occurs i n one d i r e c t i o n more than i n another s u s c e p t i b i l i t y i n one d i r e c
t i o n of a component
then i n another. Suc
general heading of texture. P l a s t i c deformation i n creases the density of d i s l o c a t i o n s and these may play
an important r o l e i n crack propagation. For heat
treatable a l l o y s that s u f f e r from stress corrosion,
s u s c e p t i b i l i t y i s usually increased by increasing the
strength. F i n a l l y , the path of a crack may be transgranular or intergrandular. In some a l l o y s i t i s
predominently one, i n others mixed, i n other dependent
upon the environment or the l e v e l of s t r e s s . Observations i n crack path provide information about the
mechanisms since they indicate the r e l a t i v e importance
of s t r e s s , chemistry, a l l o y composition, etc.
Electrochemistry.
In aqueous solutions containing
dissolved, charged species, electrochemical reactions
occur on metal surfaces and the rates at which they
occur w i l l a f f e c t the s u s c e p t i b i l i t y of an a l l o y to
stress corrosion cracking. The most important v a r i a b l e
i s the corrosion p o t e n t i a l of the specimen, a r i s i n g
from p o l a r i z a t i o n of the separate anode and cathode
reactions to a common value. Changes i n p o t e n t i a l w i l l
always a f f e c t stress corrosion reactions.
Conductivity,
pH, O 2 l e v e l s , s o l u t i o n composition and temperature are
also important.
Fracture Mechanics. The manner i n which a s p e c i men i s stressed may a f f e c t stress corrosion susceptib i l i t y . A condition of plane s t r a i n , achieved when the
specimen thickness i s above a c e r t a i n value which i s
related to i t s strength (5) , may sometimes promote
greater s u s c e p t i b i l i t y than i s observed i n specimens
below that thickness. Crack branching can sometimes be

324
CORROSION
CHEMISTRY
predicted from consideration of s t r a i n energy release

rate (2). The sharpness of cracks (notch root radius)
i s important. Blunt cracks can be expected to propagate
less r e a d i l y than sharp cracks. Crack or notch depth i s
also important from the viewpoint of stress concentra
t i o n . The a p p l i c a t i o n of a c r i t i c a l flaw depth c r i t e r i o n
i s sometimes attempted. Loading mode i s also c r i t i c a l ,
being the r e l a t i o n between the d i r e c t i o n s of applied
stress and the plane of cracking.
Systems of Stress Corrosion
Cracking
Stress corrosion cracking i s often described as

a r i s i n g between an a l l o y and a s p e c i f i c environment.
F a i l u r e s of -brass i n ammoniacal solutions would be a
t y p i c a l example. However, i t has become increasingly
c l e a r i n recent year
corrosion cracking ca
ment. The s p e c i f i c aspect of the corrodent i s therefore
no longer true. Nevertheless, only a small number of
corrodents cause stress corrosion i n any a l l o y . What
needs to be explained i s what property or action of a
corrodent i s necessary to promote stress corrosion.
An
attempt to answer t h i s question i s made below i n the
discussion on mechanisms. With these reservations, a
l i s t of stress corrosion cracking systems (alloy +
corrodent) i s given i n Table I, which i s not intended
to be complete, merely to indicate the more commonly
observed types of f a i l u r e s .
Testing f o r Stress Corrosion S u s c e p t i b i l i t y
Most stress corrosion service f a i l u r e s occur from
the influence of r e s i d u a l stresses. These a r i s e during
component manufacture, and plant assembly, including
welding. In laboratory work the stress i s usually
applied e x t e r n a l l y since i t i s then much easier to con
t r o l and measure. The oldest and simplest t e s t i s to
measure how long a specimen takes to break the timet o - f a i l u r e , t f . Typical specimens might be loaded i n
tension and surrounded by the corrodent or bent into a
U, clamped and then immersed. T y p i c a l l y , the value t
varies as shown i n Figure 1. Two points can be made.
F i r s t , the t f changes l e s s markedly at stresses above
the 0.1% proof stress than below i t . Secondly, i t i s
not always c l e a r whether a threshold stress e x i s t s
below which stress corrosion f a i l u r e s w i l l not occur.
This i s of obvious importance but i t has proved a

10.
SCULLY
Table I
Stress-Corrosion
Cracking
325
A l l o y / E n v i r o n m e n t Systems E x h i b i t i n g
Corrosion Cracking
Stress
Alloy
Environment
Mild steel
Ho
High s t r e n g t h s t e e l s
Aqueous e l e c t r o l y t e s , p a r t i c u
l a r l y when c o n t a i n i n g ^ S
Austenitic
steels
H o t , cone, c h l o r i d e s o l u t i o n s ,
c h l o r i d e - c o n t a m i n a t e d steam
stainless
High N i a l l o y s
H i g h p u r i t y steam
-brass
Ammoniacal
Al alloys
Aqueous, C l ~ , Br"" and I

tions
Ti alloys
Aqueous C I , B r and I s o l u
t i o n s ; organic l i q u i d s , N 0^
solutions
solu
Mg a l l o y s
Aqueous C I /CrO^
solutions
Zr a l l o y s
Aqueous C l ~ s o l u t i o n s ;
l i q u i d s , I S) 350C
organic

CORROSION
326
CHEMISTRY
d i f f i c u l t point to e s t a b l i s h . Some stress corrosion

systems have such a threshold, others do not. The
point i s further discussed below.
In examining a l l the m e t a l l u r g i c a l and e l e c t r o
chemical variables that together determine suscepti
b i l i t y , the measurement of t f i s not a l t o g e t h e r ^ s a t i s
factory since changes i n t f can a r i s e f o r two d i f f e r e n t
reasons. Time-to-failure i s made up of two components,
the time f o r the crack to i n i t i a t e (t^) and the time
for i t to propagate ( t ) so that
t. + t
= t
(1)
Whether the e f f e c t of a changed v a r i a b l e on t f

a r i s e s from a l t e r a t i o n s to t i or tp may be of funda
mental s i g n i f i c a n c e and i t i s therefore important under
some circumstances
between the component
that t i i s of greater consequence than tp (a) because
i t i s frequently the case that t i >> tp, and (b) be
cause i t would seem self-evident that what cannot
i n i t i a t e cannot propagate. In p r a c t i c e , however, such
considerations are too simple. I t i s generally well
recognized that engineering structures composed o f a
number o f metal components always contain a m u l t i p l i
c i t y o f surface cracks and flaws. These a r i s e during
f a b r i c a t i o n and assembly. I f any of these i s an
i n c i p i e n t stress corrosion crack, the considerations of
i n i t i a t i o n are unimportant because they are i r r e l e v a n t .
What then becomes important i s whether the crack w i l l
propagate and a t what rate.
Such considerations have given r i s e to the use of
precracked notched specimens, l i k e those that are used
i n measuring a m e t a l l u r g i c a l f a c t o r known as Fracture
Toughness (5). The dimensions of such specimens are
determined Ey considerations of Fracture Mechanics.
This approach tends to be l i m i t e d to high strength
a l l o y s since these often have mechanical properties
that are c l o s e s t to the i d e a l required and because of
t h e i r engineering importance. The type of specimem
employed takes into account the stress concentration
a r i s i n g from the presence of a crack i n a specimen and
employs a measured component K, the stress i n t e n s i t y
factor, which i s obtained from the applied stress
d / 2 , where c i s the crack depth. I t has units
\~3/2. I f such specimens are now tested as a func
t i o n of t i m e - t o - f a i l u r e , the r e s u l t s obtained are of
the kind shown i n Figure 2. A g a i n the question a r i s e s
of a threshold which i s such specimens i s termed K -
where the subscript I r e f e r s to the loading mode(5) .
The whole term represents that value of below
r
SCC

10.
SCULLY
Figure 1.
Stress-Corrosion
Cracking
327
Relationships between time-to-failure (t ) and applied stress () com

monly observed in stress-corrosion cracking
f
Klc
CO
LU
sec
CO
CO
LU
CC
TIME TO FAILURE
Figure 2. Retionship between t and

initial value of stress intensity factor (K)

328
which f a i l u r e does not occur. Since the i n i t i a t i o n

time i s very small i n r e l a t i o n to t f (the reverse of
the type of experiment to which Figure 1 a p p l i e s ) , t h i s
t e s t gives a good i n d i c a t i o n of stress corrosion crack
propagation r e s i s t a n c e . The r a t i o of K j .
to K j
(the fracture toughness i n a i r ) i s a u s e f u l r a t i o of
r e l a t i v e s u s c e p t i b i l i t y . For T i a l l o y s , f o r example,
i t v a r i e s between 0.2-0.9, which could be said to
describe a l l o y s that are very susceptible to those that
are scarcely susceptible.
Since t h i s type of t e s t i s mainly concerned with
propagation, a t t e n t i o n was subsequently focused upon
measuring v e l o c i t y as a function of K. A general
schematic p i c t u r e of r e s u l t s obtained i s shown i n
Figure 3. A maximum of 3 stages of cracking may be
observed.
Stage I (the extent of which w i l l be deter
mined by the d i f f e r e n c
at the Stage I / I I t r a n s i t i o n
dence of crack v e l o c i t y upon K. For A l and T i a l l o y s
an a c t i v a t i o n energy f o r t h i s stage of 112 kJ*mol~1 has
been determined (2). Stage I I , sometimes referred to
as the plateau v e l o c i t y , i s generally interpreted as
being caused by the chemical or electrochemical reac
t i o n at the crack t i p being l i m i t e d by d i f f u s i o n of a
c r i t i c a l reactant or product within the s o l u t i o n .
The
idea i$ supported by observations (2) that increasing
the s o l u t i o n v i s c o s i t y lowers the plateau v e l o c i t y .
An
example of t h i s i s shown i n Figure 4 (2). An a c t i v a
t i o n energy of 12-21 kJmol" f o r t h i s region has been
obtained both f o r A l and T i a l l o y s . Stage I I I i s r a r e l y
observed and a r i s e s mainly f o r mechanical reasons.
For
many a l l o y s , therefore, Figure 3 would c o n s i s t of
Stages I and II only.
This type of experimental data has been of con
siderable value. I t has become possible to examine a l l
the major v a r i a b l e s , one at a time, f o r t h e i r e f f e c t
upon crack v e l o c i t y . As a r e s u l t , i t becomes p o s s i b l e ,
i f required, to determine i n d e t a i l the e f f e c t of
minute v a r i a t i o n s i n composition, changes i n heat
treatment, electrochemical v a r i a b l e s and changes to the
environment. Typical examples are shown i n Figures 5,
6, and 7 (2).
When such data are a v a i l a b l e , they can be used i n
a l l o y s e l e c t i o n . Stress corrosion s i t u a t i o n s cannot
always be avoided. Under such circumstances a l l o y s
which have a low plateau maximum v e l o c i t y can be chosen
i n preference to a l l o y s with a high plateau v e l o c i t y
under circumstances where the same a l l o y s are metallurg i c a l l y equivalent or interchangeable. Examples of
t h i s have been given i n the l i t e r a t u r e (5).
s c c

10.
SCULLY
Stress-Corrosion
Cracking
329
<
oc
II
CO
oc
DC !=

Co
CO LU
LU
>
DC
hco
Klc
STRESS INTENSITY,
Figure 3.
General relationship between stress-corrosion-crack velocity (v) and

stress intensity factor (K)

330
STRESS INTENSITY, (kg.mm" )

3/2
0
"
icf
100
20
40
60
80
1
1 1
1
1 1
ALLOY 7079-T651
2.5 cm THICK PLATE
CRACK ORIENTATION TL
2 MOLAR KI SOLUTION (HoO+GLYCEROL)
TEMPERATURE 23 *C
POTENTIAL-450 mVvsE +
u
/u
VISCOSITY (CENTIPOISE)
10"
10"
7.2
/
"
24
H^QOOOOOOOO
68
417
/Zdoooo
10"
10"
icf
I
J
1
10
1 1
10
15
20 25
30
STRESS INTENSITY, (MN/m )

3/2
N.A.T.O.
Figure 4.
The effect of solution viscosity upon the log v:K relationship of an

aluminium alloy (2)

10.
SCULLY
Stress-Corrosion
331
Cracking
STRESS INTENSITY
(kg-mm
20
40
60
80
J
1
J
1
1
3/2
1 0
, 0
-7i
10"
13
I
0
)
100
1
A L L O Y 7178 - T651 + O V E R A G E D AT 1 6 0 C
2.5 cm THICK PLATE
CRACK ORIENTATION T L
SATURATED AQUEOUS NaCI SOLUTION
OPEN CIRCUIT
TEMPERATURE 2 3 C
I
5
I
I
I
I
10
15
20
25
STRESS INTENSITY (MN/m )
I
30
3/2
N.A.T.O.
Figure 5.
Effect of overaging on stress-corrosion-crack velocity in an aluminum

alloy (2)

ACIDIC
>
INCREASING pH
POTENTIAL
N.A.T.O.
Figure 6.
Schematic of the influence of pH on stress-corrosion-crack velocity in

titanium alloys (2)

SCULLY
Stress-Corrosion
-3
10
20
333
Cracking
STRESS INTENSITY (kg. mm

40
60
I
-3/2,
100
10
8mNaI
5mKI
10
0.5 m
tz 10
0.2 m
0.1 m
0.05 m
r7
10
0.02 m
0.002m and
DISTILLED WATER
10
10
10
ALLOY 7079-T651
2.5 cm THICK PLATE
CRACK ORIENTATION TL
AQUEOUS IODIDE SOLUTIONS
POTENTIAL- 450 mV vs ,+
TEMPERATURE 23 'C
2
pH* 6
10
10
15
20
25
30
3/2
STRESS INTENSITY (MN/m)
4
N.A.T.O.
Figure 7.
Effect of solution concentration upon stress-corrosion-crack velocity in

an aluminum alloy (2)

334
The
Importance o f
Repassivation
I n many o f t h e a l l o y systems shown i n T a b l e I , t h e

s t a b l e c o n f i g u r a t i o n of the a l l o y s u r f a c e i s t h a t i t i s
f i l m e d . Many o f t h e a l l o y s , e.g., s t a i n l e s s s t e e l s , A l ,
T i , Zr and Mg a l l o y s a r e o n l y u s a b l e i n such a c o n d i tion.
Such a c o n s i d e r a t i o n a p p l i e s n o t o n l y t o t h e s e
a l l o y s covered w i t h a t h i n p a s s i v e f i l m but a l s o t o
t h o s e on w h i c h r e l a t i v e l y t h i c k f i l m s a r e formed.
The
p o s s i b l e mechanisms by w h i c h s t r e s s c o r r o s i o n c r a c k i n g
o c c u r s a r e c o n c e r n e d w i t h r e a c t i o n s between u n f i l m e d
m e t a l and t h e e n v i r o n m e n t . B e f o r e c o n s i d e r a t i o n o f
t h e s e i t i s n e c e s s a r y t o c o n s i d e r how t h e s e v a r i o u s
t y p e s o f f i l m b r e a k down i n i t i a l l y . W h i l e many o f t h e
a l l o y s e x h i b i t p i t t i n g , i t i s not necessary f o r p i t t i n g
as such t o p r e c e d e c r a c k p r o p a g a t i o n
P i t t i n g i s assoc i a t e d with s t a t i c unstresse
i s associated with a
The a p p l i c a t i o n o f a s t r e s s c r e a t e s a s u r f a c e s t r a i n r a t e (or c r e e p s t r a i n - r a t e , s i n c e i t i s v e r y l o w ) .
Of
f u n d a m e n t a l i m p o r t a n c e i s t h e i n t e r a c t i o n o f t h e def o r m i n g s u r f a c e and t h e r e a c t i o n s on t h e m e t a l s u r f a c e .
The s u b j e c t i s n o t a s i m p l e one, b u t t h e main p o i n t s
can b e s t be e n v i s a g e d by a t t e m p t i n g t o draw t h e r e p e t i t i v e segment o f e v e n t s o c c u r r i n g a t a c r a c k t i p o r a t
t h e base o f a s u r f a c e f l a w . T h i s i s a t t e m p t e d i n
F i g u r e 8.
The a p p l i c a t i o n o f a s t r e s s c r e a t e s a s l i p
step which breaks the p a s s i v e f i l m which i s i n
e q u i l i b r i u m w i t h t h e s o l u t i o n . There i s abundant
e x p e r i m e n t a l e v i d e n c e t h a t such e v e n t s t a k e p l a c e
(e.g., 6).
The s l i p s t e p h e i g h t w i l l u s u a l l y be v e r y
much g r e a t e r t h a n t h e f i l m t h i c k n e s s and t h e f i l m i s
usually relatively b r i t t l e .
B o t h t h e s e would appear
t o be n e c e s s a r y c o n d i t i o n s f o r t h e s i t u a t i o n d e p i c t e d
i n F i g u r e 8. A f t e r f i l m f r a c t u r e , r e a c t i o n t h e n o c c u r s
between t h e newly c r e a t e d m e t a l s u r f a c e and t h e e n v i ronment. The s p e c i f i c t y p e o f r e a c t i o n w i l l be
c o n s i d e r e d below s i n c e i t i s t h e i m p o r t a n t p r o c e s s t h a t
determines crack propagation.
But t h e t i m e a v a i l a b l e
f o r t h i s r e a c t i o n t o o c c u r w i l l be d e t e r m i n e d by t h e
r e p a i r t i m e o f t h e f i l m , commonly r e f e r r e d t o as t h e
r e p a s s i v a t i o n t i m e (7).
As soon as t h e f i l m f r a c t u r e s ,
i t w i l l s t a r t t o reform s i n c e the e q u i l i b r i u m c o n d i t i o n
o f t h e s u r f a c e i s t h a t i t i s f i l m e d . I t has been argued
(7) t h a t t h e d e l a y i n r e p a s s i v a t i o n i s o f c r u c i a l importance.
I f r e p a s s i v a t i o n occurs too r a p i d l y , there
w i l l n o t have been t i m e f o r enough r e a c t i o n t o o c c u r t o
cause an i n c r e m e n t o f c r a c k growth. I f r e p a s s i v a t i o n
o c c u r s t o o s l o w l y , t h e n t o o much r e a c t i o n may have
o c c u r r e d , g i v i n g r i s e t o c r a c k b l u n t i n g and p i t t i n g .

SCULLY
Stress-Corrosion
Cracking
335
Figure 8. Schematic of the sequence of events occurring at the tip of a propagat

ing stress-corrosion crack. The film is fractured (B) and immediately starts to
repair (C) while dissolution is occurring. Complete repassivation occurs at D by
which time the crack has extended.

CORROSION
336
CHEMISTRY
The i m p o r t a n t f a c t o r i s t h e r e p a s s i v a t i o n time s i n c e i t
d e t e r m i n e s f o r how l o n g t h e m e t a l and e n v i r o n m e n t c a n
react together.
F i g u r e 8 c a n be c o n s i d e r e d i n a more g e n e r a l sense.
The p l a s t i c d e f o r m a t i o n t h a t c r e a t e s t h e s l i p s t e p c a n
be c o n s i d e r e d as a s t r a i n - r a t e t h a t , i n t h e most gene r a l way, i s c r e a t i n g new, u n f i l m e d , m e t a l s u r f a c e . I t
w i l l be governed by m e c h a n i c a l and m e t a l l u r g i c a l
f a c t o r s . The p r o c e s s t h a t c a u s e s f i l m f o r m a t i o n i s
e l e c t r o c h e m i c a l and i t w i l l be dependent upon t h e
p o t e n t i a l and a l l o t h e r e l e c t r o c h e m i c a l f a c t o r s .
It is
possible to consider that stress corrosion cracking
o c c u r s when t h e r e i s a c r i t i c a l imbalance between t h e s e
two r a t e p r o c e s s e s one c r e a t i n g f r e s h m e t a l a r e a ,
t h e o t h e r f i l m i n g t h a t a r e a . Thus, t h e s i t u a t i o n dep i c t e d s c h e m a t i c a l l y i n F i g u r e 8 i s n o t merely t h a t o f
a f i l m b r o k e n by a
be e x p e c t e d , and i
a l l o y s and m e t a l s i n e n v i r o n m e n t s t h a t a r e known n o t t o
cause s t r e s s c o r r o s i o n c r a c k i n g . What i s e n v i s a g e d i n
F i g u r e 8 i s a p a r t i c u l a r s e t o f circumstances i n which
p a s s i v a t i o n i s d e l a y e d f o r a narrow range o f t i m e i n t e r vals.
A good example o f t h e i m p o r t a n c e o f r e p a s s i v a t i o n
i s shown i n F i g u r e 9 (8). A t i t a n i u m a l l o y , T i - 5 A l 2.5 Sn, i n t h e form o f t e n s i l e specimens i s s t r a i n e d
d y n a m i c a l l y i n two d i f f e r e n t s o l u t i o n s .
I n aqueous
NaCl s o l u t i o n T i does n o t c o r r o d e and r e p a s s i v a t i o n c a n
be e x p e c t e d t o o c c u r . A t h i g h c r o s s h e a d speeds t h e
t e s t ' i s o v e r i n a v e r y s h o r t t i m e and t h e r e i s no t i m e
for crack i n i t i a t i o n .
A f r a c t u r e i s observed f r a c t o graphically with the elongation t o fracture
and t h e
t e x t u r e t h e same as i n a i r . A t l o w e r c r o s s h e a d speeds
s t r e s s c o r r o s i o n c r a c k propagation occurs w i t h a consequent r e d u c t i o n i n f and c h a r a c t e r i s t i c c l e a v a g e
f r a c t o g r a p h y . A t t h e l o w e s t c r o s s h e a d speeds t h e
r e l a t i v e l y s l o w s t r a i n - r a t e i n d u c e d on t h e s u r f a c e i s
such t h a t r e p a s s i v a t i o n p r e d o m i n a t e s o v e r c r a c k i n g and
no c r a c k p r o p a g a t i o n o c c u r s . F r a c t o g r a p h i c a l l y , a i r
f r a c t u r e i s seen and e i s h i g h . Thus, i n t h e aqueous
s o l u t i o n c r a c k i n g i s c o n f i n e d t o a narrow range o f
speeds. T h i s b e h a v i o r c a n be c o n t r a s t e d w i t h t h a t obs e r v e d f o r t h e same a l l o y exposed t o a CH3OH + 1 v o l . %
cone HC1 m i x t u r e w h i c h i s c o r r o s i v e t o T i and i n w h i c h ,
t h e r e f o r e , no r e p a s s i v a t i o n m i g h t be e x p e c t e d .
At high
c r o s s h e a d speeds t h e same b e h a v i o r i s seen as t h a t
o b s e r v e d i n t h e aqueous s o l u t i o n . A t t h e l o w e s t c r o s s head s p e e d s , however, because no r e p a s s i v a t i o n i s
p o s s i b l e , c r a c k i n g i s o b s e r v e d and because t h e t e s t
t a k e s i n c r e a s i n g l y l o n g t i m e s as t h e c r o s s h e a d speed i s
f

10.
SCULLY
Stress-Corrosion
337
Cracking
16h
Corrosion Science
Figure 9. The rehtionship between elongation-to-failure (e ) and crosshead speed
for a Ti-5Al-2.5Sn
alloy exposed to (1) aqueous NaCl, and (2) a
CH OH/HCl
mixture (8)
f

CORROSION
338
CHEMISTRY
l o w e r e d , the f f a l l s c o n t i n u a l l y . I t can be e x p e c t e d
t h a t t h e c r a c k v e l o c i t y would f a l l u n t i l i t became
s i m i l a r t o the c o r r o s i o n r a t e o f the u n s t r e s s e d a l l o y
w h i c h , i n t h i s example, i s s e l e c t i v e l y i n t e r g r a n u l a r .
I n t h e CH3OH s o l u t i o n no K j
o r any o t h e r t h r e s h o l d
can be a n t i c i p a t e d and i t i s not found. I n the aqueous
solution a K i
can be e x p e c t e d , c o r r e s p o n d i n g t o
t h a t v a l u e o f t h a t r e s u l t s i n so low a s u r f a c e s t r a i n r a t e t h a t r e p a s s i v a t i o n can o c c u r .
This s t r a i n - r a t e
has been c h a r a c t e r i z e d
(SO . K j
i s commonly
o b s e r v e d i n T i a l l o y s exposed t o aqueous c h l o r i d e s o l u
t i o n s . From F i g u r e 9 and a l l t h a t has been d e s c r i b e d ,
i t can be a p p r e c i a t e d t h a t K i
i s not a m a t e r i a l
constant.
F o r a g i v e n a l l o y i t v a r i e s a c c o r d i n g t o the
e n v i r o n m e n t i n w h i c h i t i s measured. I t i s not an
a l l o y t h a t has a t h r e s h o l d ; i t i s the a l l o y + e n v i r o n
ment w h i c h may e x h i b i
The t y p e o f e x p e r i m e n encompasse
Figur
become i n c r e a s i n g l y i m p o r t a n t as a method o f t e s t i n g .
The c o n d i t i o n s a r e s e v e r e , t h e t e s t s a r e r a p i d and t h e
imposed c o n d i t i o n s o f a s l o w s t r a i n - r a t e a r e s i m i l a r t o
those o c c u r r i n g at a crack t i p . For reasons d i s c u s s e d
below, e x p e r i m e n t s s h o u l d be done p o t e n t i o s t a t i c a l l y . A
r e c e n t c o n f e r e n c e (1_0) was d e v o t e d t o t h e c o n s t a n t
e x t e n s i o n r a t e t e s t , o r g a n i z e d by A.S.T.M.
The i m p o r t a n c e o f r e p a s s i v a t i o n and t h e i n t e r a c
t i o n of t h i s process with a s t r a i n i n g metal surface
p r o b a b l y c o n s t i t u t e s t h e e s s e n s e o f many s t r e s s c o r r o
s i o n c r a c k i n g mechanisms. S i n c e r e p a s s i v a t i o n i s an
e l e c t r o c h e m i c a l phenomenon, i t m i g h t be e x p e c t e d t h a t
the necessary imbalance to achieve s t r e s s c o r r o s i o n ,
r e f e r r e d t o above, w i l l o c c u r o n l y o v e r a narrow range
o f p o t e n t i a l , c o r r e s p o n d i n g t o a narrow range o f r e
p a s s i v a t i o n r a t e s . Such r a t e s can be e x p e c t e d t o
change m a r k e d l y i n t h o s e r e g i o n s o f p o t e n t i a l where t h e
p a s s i v e range changes t o a p i t t i n g range o r t o an
a c t i v e r a n g e , i . e . , where the f i l m i s c h a n g i n g from
b e i n g t h e s t a b l e s u r f a c e c o n f i g u r a t i o n t o where i t i s
an u n s t a b l e c o n f i g u r a t i o n . The zones o f p o t e n t i a l
where c r a c k i n g m i g h t be e x p e c t e d a r e shown i n F i g u r e 10.
There a r e examples i n t h e l i t e r a t u r e o f c r a c k i n g
o c c u r r i n g i n such r e g i o n s (2^) . The s i t e o f t h e s e
r e g i o n s depends upon a number o f e l e c t r o c h e m i c a l
f a c t o r s . S t r e s s c o r r o s i o n f a i l u r e o c c u r s under openc i r c u i t c o n d i t i o n s when t h e c o r r o s i o n p o t e n t i a l o f an
a l l o y l i e s w i t h i n the p o t e n t i a l range f o r c r a c k i n g o f
t h a t a l l o y i n the p a r t i c u l a r e n v i r o n m e n t . Systems de
s c r i b e d i n Table I f a l l i n t o t h i s category.
I t must be
emphasized t h a t under c o n t r o l l e d p o t e n t i a l c o n d i t i o n s
s t r e s s c o r r o s i o n f a i l u r e may o c c u r i n a l l o y s exposed t o
s

10.
SCULLY
Stress-Corrosion
Cracking
339
e n v i r o n m e n t s w h i c h do n o t cause f a i l u r e under open c i r

c u i t c o n d i t i o n s , -brass f a i l s i n ammonia under open
c i r c u i t c o n d i t i o n s , as i s i n d i c a t e d i n T a b l e I . When
a n o d i c a l l y p o l a r i z e d , i t a l s o c r a c k s i n n i t r a t e and
s u l f a t e s o l u t i o n s . Thus, the u n i q u e n e s s o f ammonia
l i e s o n l y i n i t s a b i l i t y t o cause c r a c k i n g under open
c i r c u i t c o n d i t i o n s under a wide range o f s o l u t i o n pH
c o n d i t i o n s ( o t h e r s o l u t i o n s , e.g., t a r t r a t e s o l u t i o n s ,
can a l s o cause c r a c k i n g o v e r a narrow range o f pH).
T h i s t y p e o f o b s e r v a t i o n a p p l i e s t o o t h e r systems too
and i t s i m p o r t a n c e c a n n o t be e x a g g e r a t e d . I t has a
b e a r i n g b o t h on m e c h a n i s t i c i v e s t i g a t i o n s and on t e s t
i n g p r o c e u d r e s . I t i s f o o l i s h t o t e s t o n l y under open
c i r c u i t conditions s i n c e , i f cracking occurs i n a poten
t i a l range n o t i n c l u d i n g the open c i r c u i t p o t e n t i a l ,
s u s c e p t i b i l i t y w i l l be m i s s e d i n l a b o r a t o r y c o n d i t i o n s .
I f i n s e r v i c e use th
the c r a c k i n g r a n g e ,
appear t o be a s i m p l e p o i n t , but such problems do a r i s e
and cause c o n f u s i o n .
T e s t i n g s h o u l d a l w a y s be done
o v e r a range o f p o t e n t i a l l a r g e r t h a n t h a t l i k e l y t o be
e n c o u n t e r e d i n s e r v i c e under the most extreme c o n d i
tions .
R e p a s s i v a t i o n p r o c e s s e s have become an i m p o r t a n t
s u b j e c t i n s t r e s s c o r r o s i o n s t u d i e s and a l s o i n o t h e r
forms o f c o r r o s i o n , e.g., p i t t i n g c o r r o s i o n and c o r r o
s i o n f a t i g u e . A range o f s c r a t c h i n g and s t r a i n i n g
e l e c t r o d e t e c h n i q u e s have been employed. W h i l e i t i s
n o t p o s s i b l e t o go i n t o d e t a i l , t h e r e s u l t s have t o be
examined i n r e l a t i o n t o t h e t e c h n i q u e s employed, e.g.,
has r e p a s s i v a t i o n s t a r t e d b e f o r e t h e s c r a t c h i n g o r
s t r a i n i n g has stopped? I t i s i m p o r t a n t a l s o t o know
whether t h e c u r r e n t measured under p o t e n t i o s t a t i c
c o n d i t i o n s i s a c o m p l e t e anode c u r r e n t o r t h e d i f f e r
ence between an anode c u r r e n t and a c a t h o d e c u r r e n t
(most commonly due t o H i o n r e d u c t i o n ) . T y p i c a l r e
p a s s i v a t i o n r a t e s c o r r e s p o n d t o an e q u a t i o n (11) o f
the t y p e :
+
i - i
(i - i )t~
1
(2)
where i = c u r r e n t a f t e r t i m e t , Q = c u r r e n t a f t e r comp l e t e r e p a s s i v a t i o n , i-j = c u r r e n t a f t e r one second and

b i s a constant.
The c o n s t a n t b v a r i e s w i t h p o t e n t i a l .
Under c e r t a i n c o n d i t i o n (11) the r e l a t i o n s h i p s i s g i v e n
by
i = i
max
exp(-gt)

(3)
340
where 3 i s a c o n s t a n t , and i
i s t h e i n i t i a l maximum
value of the c u r r e n t a f t e r d e s t r u c t i o n of the f i l m .
When a f i l m i s b r o k e n , t h e i n i t i a l monolayer a d s o r b s
w i t h i n 20-50 ms ( 1 2 ) . The measured c u r r e n t i s made up
p a r t l y o f d i s s o l u t i o n and p a r t l y o f f i l m f o r m a t i o n ,
t h e r a t i o between them f a l l i n g w i t h t i m e .
m
S t r e s s C o r r o s i o n Mechanisms
The c i r c u m s t a n c e s under w h i c h t h e f i l m i s b r o k e n
and r e p a i r e d have been d e s c r i b e d a t l e n g t h s i n c e t h e y
c o n t r o l the subsequent r e a c t i o n t i m e d u r i n g w h i c h t h e
c r a c k a c t u a l l y grows. I t has been s t r o n g l y emphasized
s i n c e u n l e s s t h i s p o i n t i s u n d e r s t o o d c o n f u s i o n can
a r i s e because t h e a l t e r a t i o n o f an e x p e r i m e n t a l v a r i a b l e , e.g., p o t e n t i a l o r pH may have a g r e a t e r e f f e c t
on r e p a s s i v a t i o n t h e
less that p o s s i b i l i t
i n t e r p r e t a t i o n i s l i k e l y t o a r i s e on o c c a s i o n .
An
example i s g i v e n below w i t h r e s p e c t t o t h e e f f e c t o f
c a t h o d i c p o l a r i z a t i o n on s t r e s s c o r r o s i o n c r a c k i n g o f
T i a l l o y s i n aqueous c h l o r i d e s o l u t i o n s . I t i s a
g e n e r a l p o i n t and i s not o f t e n emphasized.
The Mechanism o f
Cracking
Why does c r a c k i n g o c c u r ? T h i s i s t h e most d i f f i c u l t q u e s t i o n t o answer. Many e x p l a n a t i o n s have been

put f o r w a r d and w i t h s t r e s s c o r r o s i o n c r a c k i n g o c c u r r i n g i n so many a l l o y s i t i s not u n l i k e l y t h a t some
v e r y s p e c i f i c p o i n t s a p p l y h e r e and t h e r e . An example
might be t h e a c t i o n o f v o l u m i n o u s c o r r o s i o n p r o d u c t i n
wedging open a c r a c k f o r w h i c h t h e r e i s e v i d e n c e i n
i s o l a t e d cases.
O v e r r i d i n g many such t i n y phenomenol o g i c a l p o i n t s , c r a c k i n g mechanisms can be d i v i d e d
i n t o (1) a c t i v e p a t h , (2) hydrogen e m b r i t t l e m e n t ,
(3)
s t r e s s s o r p t i o n and (4) c o r r o s i o n f i l m f r a c t u r e .
I t i s now i n t e n d e d t o d i s c u s s t h e e s s e n t i a l f e a t u r e s o f t h e s e mechanisms. I t must be emphasized t h a t
t h e s e a r e g e n e r a l c a t e g o r i e s and much s u b d i v i s i o n i s
p o s s i b l e , p a r t i c u l a r l y i n t h e c a s e o f hydrogen emb r i t t l e m e n t . There i s no r e a s o n t h a t c r a c k i n g s h o u l d
not o c c u r by a mechanism t h a t t r a v e r s e s more t h a n one
o f t h e above, e.g., a c o m b i n a t i o n o f a n o d i c d i s s o l u t i o n and hydrogen e m b r i t t l e m e n t . These f o u r c a t e g o r i e s
a r e i n no way e x c l u s i v e from each o t h e r .
A c t i v e Path.
Since the term s t r e s s c o r r o s i o n
c r a c k i n g i m p l i e s c o r r o s i o n , i t i s not s u r p r i s i n g t h a t
t h e f i r s t mechanism e v e r p r o p o s e d was t h a t c r a c k i n g

10.
SCULLY
Stress-Corrosion
341
Cracking
o c c u r r e d by p r e f e r e n t i a l d i s s o l u t i o n o v e r a narrow p r e f e r r e d f r o n t a l o n g a p a t h t h a t was p r e - e x i s t i n g ( 1 3 ) .
T h i s was p r o b a b l y t r u e f o r t h e p a r t i c u l a r system Eing
i n v e s t i g a t e d , but s i n c e c r a c k i n g occurs i n a l l o y s which
most c e r t a i n l y do n o t have a p r e - e x i s t i n g p a t h , more
r e c e n t i d e a s have a t t e m p t e d t o e x p l a i n t h e l o c a l i z e d
c o r r o s i o n by a p r o c e s s i n v o l v i n g r e p a s s i v a t i o n o f the
crack s i d e s , thus c o n c e n t r a t i n g the c u r r e n t a t the t i p
where v a r i o u s forms o f d i r e c t i o n a l l o c a l i z e d d i s s o l u t i o n occurs.
The p o s s i b l e p r e f e r e n t i a l c o r r o s i o n o f
d i s l o c a t i o n s p i l e d up a t t h e c r a c k t i p as a r e s u l t o f
t h e a c t i n g s t r e s s has been c o n s i d e r e d a t l e n g t h o v e r
many y e a r s .
The s t r a i n energy a s s o c i a t e d w i t h such
pile-ups of d i s l o c a t i o n s provides l i t t l e a d d i t i o n a l
driving force for dissolution
As a r e s u l t a t t e n t i o n has f o c u s e d on m i n u t e c o m p o s i t i o n a l changes i n a
metal l a t t i c e o c c u r r i n
w h i c h may cause s i g n i f i c a n
d i s s o l u t i o n on an a t o m i s t i c s c a l e (1_5) These i d e a s
were o r i g i n a l l y a s s o c i a t e d w i t h e l e c t r o n m i c r o s c o p e
o b s e r v a t i o n s o f t h e edges o f e l e c t r o p o l i s h e d t h i n
f o i l s where r e g i o n s o f d i s l o c a t i o n p i l e - u p s showed,
v e r y d i r e c t i o n a l d i s s o l u t i o n ( 1 6 ) . Such p r o c e s s e s
g i v e r i s e t o u n u s u a l m o r p h o l o g i c a l e f f e c t s ( V7) and
may c a u s e t u n n e l c o r r o s i o n (1_8) .
A t some s t a g e i t i s n e c e s s a r y t o know whether t h e
c u r r e n t f l o w i n g i s s u f f i c i e n t to account f o r the maximun v e l o c i t y o f t h e c r a c k , a r e q u i r e m e n t sometimes
r e f e r r e d t o as f a r a d a i c e q u i v a l e n c e .
From t h e a p p l i c a t i o n o f F a r a d a y ' s laws and assuming t h a t d i s s o l u t i o n
a c c o u n t s f o r 10095 o f t h e c r a c k p r o p a g a t i o n t h e n :
f
where = c r a c k v e l o c i t y , J - c h e m i c a l e q u i v a l e n t , F =
the F a r a d a y , = a l l o y d e n s i t y and i = d i s s o l u t i o n
current density.
F o r a number o f s t r e s s c o r r o s i o n c r a c k i n g s y s t e m s ,
e.g., m i l d s t e e l , a u s t e n i t i c s t a i n l e s s s t e e l s , measured
b a r e s u r f a c e c u r r e n t d e n s i t i e s appear t o be o f t h e
r i g h t o r d e r o f magnitude (_3) F o r o t h e r a l l o y s , e.g.,
T i a l l o y s , i n w h i c h t h e c r a c k v e l o c i t i e s a r e v e r y much
h i g h e r t h a n i n s t e e l s , much h i g h e r c u r r e n t d e n s i t i e s
are r e q u i r e d , of the order r e q u i r e d f o r e l e c t r o c h e m i c a l
m a c h i n i n g . T h e i r e x i s t e n c e has been c l a i m e d (2).
R e f e r e n c e t o F i g u r e 8, t o g e t h e r w i t h t h e c o n c e p t
of r e p a s s i v a t i o n , i n d i c a t e s d u r i n g the propagation of
c r a c k s t h e c u r r e n t s h o u l d c o n s i s t o f a number o f s u c c e s
s i v e t r a n s i e n t s . One i s shown i n F i g u r e 11, w h i c h
m i g h t be t a k e n t o c o r r e s p o n d t o t h e sequence o f e v e n t s

342
t
Figure 11. A general schematic of the current transient during the sequence of
events drawn in Figure 8. The hatched area represents the total charge flowing.

10.
SCULLY
Stress-Corrosion
Cracking
343
d e s c r i b e d i n F i g u r e 8. What i s i m p o r t a n t i s t h e t o t a l
amount o f c o r r o s i o n , r e p r e s e n t e d by t h e c h a r g e , w h i c h
i s h a t c h e d i n F i g u r e 11.
I t has been argued (9) t h a t
s t r e s s c o r r o s i o n c r a c k p r o p a g a t i o n o c c u r s as a r e s u l t
o f t h e passage o f a c o n s t a n t c h a r g e Q i / w h i c h t h e n
i n i t i a t e s t h e n e x t i n c r e m e n t o f c r a c k growth.
Crack
a r r e s t occurs i f r e p a s s i v a t i o n occurs before Q i
has
passed.
From such c o n s i d e r a t i o n s , w i t h i n t e g r a t i o n o f
the a p p r o p r i a t e r e p a s s i v a t i o n r a t e equation over the
t i m e l i m i t s between s u c c e s s i v e s l i p s t e p e v e n t s , i t
has been p o s s i b l e t o d e r i v e t h e shape o f t h e c o r r o s i o n
c u r r e n t : t i m e c u r v e s o f Stages I and I I shown i n F i g ure 3 (9) .
m
Hydrogen E m b r i t t l e m e n t .
A t t h e c r a c k t i p i n many
a l l o y s l o c a l a c i d i t y and low p o t e n t i a l s e n s u r e t h a t
hydrogen i o n d i s c h a r g
T i , Zr a l l o y s and f o
p l a i n c a r b o n s t e e l s and a l s o f o r Mg a l l o y s i n w h i c h
the c r a c k t i p s o l u t i o n i s a l k a l i n e .
The q u e s t i o n i s
whether any o f t h e s e a l l o y s c r a c k as a r e s u l t o f H
a d s o r p t i o n w h i c h o c c u r s a f t e r n e u t r a l i z a t o n has
occurred
H +
( 5 )
= ads
and b e f o r e d e s o r p t i o n has o c c u r r e d by
H
ads
H +
ads
either
= 2
H
( 6 )
or
ads - 2
H
( 7 )
i n a c i d i c s o l u t i o n s and t h e e q u i v a l e n t r e a c t i o n s a p p r o p r i a t e f o r a l k a l i n e s o l u t i o n s i n t h e c a s e o f Mg a l l o y s .
Some p r o p o r t i o n o f Hads w i l l be absorbed by t h e a l l o y
i n any s i t u a t i o n . An i m p o r t a n t r a t i o i s H (absorbed/
H (evolved) and t h i s i s l i k e l y t o be v e r y s e n s i t i v e t o
c a t h o d i c p o i s o n s i n t h e s o l u t i o n and t o c e r t a i n e l e ments w i t h i n t h e a l l o y .
C r a c k i n g i n A l and T i a l l o y s
and i n h i g h s t r e n g t h s t e e l s i s a c c e l e r a t e d by t h e
presence of c a t h o d i c poisons. T h i s i s very s t r o n g
evidence t h a t H p l a y s a r o l e i n the c r a c k i n g process.
A f t e r e n t e r i n g t h e m e t a l i t may c o l l e c t i n s i d e
t r a p s and cause d e c o h e s i o n .
I t may combine around i n c l u s i o n s and cause l o c a l r e g i o n s o f v e r y h i g h p r e s s u r e ,
r e s u l t i n g i n b l i s t e r i n g and p o s s i b l y even f i s s i o n i n g .
I n T i and Zr a l l o y s i t may form h y d r i d e s w h i c h i n t e r a c t w i t h t h e l a t t i c e , p r o m o t i n g c l e a v a g e by impeding

344
CORROSION CHEMISTRY
t h e movement o f d i s l o c a t i o n s .
The e f f e c t s o f H on t h e
m e c h a n i c a l p r o p e r t i e s o f m e t a l s i s a v e r y complex subj e c t and no a t t e m p t has been made o t h e r t h a n t o i n d i cate s e v e r a l p o s s i b l e g e n e r a l e f f e c t s . Another area
o f some d i f f i c u l t y i s t h a t t h e d i f f u s i o n r a t e s o f H
o f t e n appear t o be t o o s l o w t o a c c o u n t f o r t h e obs e r v e d c r a c k p r o p a g a t i o n r a t e s . The r e c o n c i l i n g o f
these c o n t r a r y observations c a l l s f o r c o n s i d e r a b l e
care.
S t r e s s S o r p t i o n . T h i s mechanism supposes t h a t
t h e r e a c t i o n between a s p e c i e s i n t h e environment and
t h e m e t a l atoms a t t h e c r a c k t i p can cause a r e d i s t r i b u t i o n o f e l e c t r o n s i n t h e o r b i t s o f t h e atoms so t h a t
t h e bond between them i s weakened ( 1 9 ) . I t i s n o t
p o s s i b l e t o c i t e e x p e r i m e n t a l d a t t K a t would
t
t h i s concept f o r th
absence may m e r e l y r e f l e c t t h e d i f f i c u l t i e s o f o b t a i n
i n g such d a t a .
C o r r o s i o n F i l m F r a c t u r e . A t v a r i o u s t i m e s i t has
been s u g g e s t e d t h a t t h e f r a c t u r e o f c o r r o s i o n p r o d u c t
f i l m s a t t h e c r a c k t i p w i t h t h e i r subsequent r e f o r m a t i o n c o n s t i t u t e s t h e main f o r w a r d movement o f t h e
c r a c k . The e v i d e n c e f o r such a mechanism i s n o t t e r r i b l y c l e a r . T h i c k f i l m formed on s t e e l s and b r a s s e s ,
f o r example, may form by p r e c i p i t a t i o n from s o l u t i o n
r a t h e r t h a n by d i r e c t c o r r o s i o n o f t h e m e t a l t o a
s o l i d compound. Where t h i s o c c u r s , t h e i n i t i a l d i s s o l u t i o n t h a t p r e c e d e s the p r e c i p i t a t i o n would appear
to f i t i n t o the a c t i v e path category. I f f r a c t u r e of
t h e p r e c i p i t a t e d f i l m i s n e c e s s a r y , t h e n i t becomes a
m a t t e r o f c h o i c e whether t h i s c o n s t i t u t e s a s e p a r a t e
c a t e g o r y o r a s p e c i a l c a s e o f t h e a c t i v e p a t h mechanism.
F o r m i l d s t e e l and b r a s s e s t h i s t y p e o f e x p l a n a t i o n i s
commonly a s s o c i a t e d w i t h i n t e r g r a n u l a r c r a c k i n g . What
needs t o be e x p l a i n e d i s why p r e f e r e n t i a l c o r r o s i o n o f
t h e g r a i n boundary o c c u r s . O f t e n t h i s i s a t t r i b u t e d
t o t h e p r e s e n c e w i t h i n t h e g r a i n boundary o f an u n i d e n t i f i e d element i n s o l i d s o l u t i o n w h i c h a l t e r s t h e
dissolution kinetics.
I t i s a requirement t h a t the
f i l m i s s u f f i c i e n t l y p r o t e c t i v e t o reduce t h e r e a c t i o n
r a t e t o an i n s i g n i f i c a n t v a l u e so t h a t i t s f r a c t u r e i s
n e c e s s a r y f o r t h e c r a c k p r o p a g a t i n g r e a c t i o n t o be r e initiated.
On b r a s s , f o r example, i n ammoniacal
s o l u t i o n s t h i c k f i l m s form o v e r a wide range o f pH b u t
i t i s o n l y o v e r a narrow range t h a t t h i s t y p e o f mechanism may a p p l y (2), c o r r e s p o n d i n g t o t h e f o r m a t i o n o f
a relatively protective film.

10.
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345
Cracking
D i s t i n g u i s h i n g between t h e v a r i o u s mechanisms and

how t h e y a p p l y t o v a r i o u s a l l o y systems i s n o t an easy
matter.
I t i s d i f f i c u l t t o design experiments t h a t
g i v e c l e a r unambiguous answers. R a t h e r e l e m e n t a r y
p o i n t s c a n be made i n o r d e r t o show some o f t h e d i f f i
culties.
Anodic p o l a r i z a t i o n w i l l f r e q u e n t l y shorten t f
and a l s o r a i s e t h e c r a c k v e l o c i t y t o a maximum a s s o c i
ated w i t h the onset o f simultaneous p i t propagation.
These e f f e c t s a r e n o t n e c e s s a r i l y e v i d e n c e t h a t an
a c t i v e p a t h mechanism i s o p e r a t i v e . I f t h e p o t e n t i a l
o f t h e c r a c k t i p i s such t h a t H i o n d i s c h a r g e c a n
o c c u r t h e n t h e g r e a t e r ease o f a c i d i f i c a t i o n a t t h e
c r a c k t i p as a r e s u l t o f t h e a p p l i c a t i o n o f a n o d i c
p o l a r i z a t i o n may i n c r e a s e t h e amount o f hydrogen
a b s o r p t i o n and t h e r e b y i n c r e a s e t h e c r a c k v e l o c i t y i f
a hydrogen e m b r i t t l e m e n
v e r s e l y , anodic p o l a r i z a t i o
applie
r e s u l t s i n a lower crack v e l o c i t y i n n e u t r a l s o l u t i o n s
(20) when t h e p o t e n t i a l i s r a i s e d i n t o t h e r e g i o n
wEere t h e f i l m t h a t forms under open c i r c u i t c o n d i
t i o n s i s u n s t a b l e . The same c u r r e n t i s t h e r e b y s p r e a d
o v e r a much w i d e r a r e a , g i v i n g r i s e t o a much h i g h e r
c r a c k d e n i s t y . The c r a c k v e l o c i t y i s t h e r e f o r e r e
duced. I n t h i s system an a c t i v e p a t h mechanism i s
o p e r a t i v e , y e t c r a c k v e l o c i t y i s reduced by a n o d i c
polarization.
Such c o n t r a r y i n t e r p r e t a t i o n s need n o t
be c o n f u s i n g . They s e r v e t o u n d e r l i n e t h a t i t i s
n e c e s s a r y t o l o o k c l o s e l y a t t h e consequences o f a
g i v e n e x p e r i m e n t a l t e c h n i q u e . T h i s c a n be p a r t i c u
l a r l y important f o r workers attempting t o i n t e r p r e t
r e s u l t s o b t a i n e d w i t h one t e c h n i q u e on two q u i t e
different alloys.
Cathodic p o l a r i z a t i o n w i l l g e n e r a l l y shorten t f
f o r a l l o y s t h a t a r e s u s c e p t i b l e t o hydrogen e m b r i t t l e
ment. T h i s i s n o t u n i v e r s a l l y t r u e , however. I f
c r a c k i n g i s o c c u r r i n g j u s t below ( F i g u r e 1 0 ) ,
then c a t h o d i c p o l a r i z a t i o n w i l l a c c e l e r a t e t h e r e p a s s i
v a t i o n p r o c e s s . T h i s i s n o t a case o f c a t h o d i c pro
tection lowering the corrosion p o t e n t i a l to the
e q u i l i b r i u m p o t e n t i a l o f t h e anode r e a c t i o n . F o r T i
a l l o y s t h e a b s o r p t i o n o f hydrogen o c c u r s r e a d i l y on
u n f i l m e d s u r f a c e s . On f i l m e d s u r f a c e s hydrogen e n t r y
i s v e r y much reduced because t h e p a s s i v e f i l m has a
low hydrogen p e r m e a b i l i t y . A l s o , t h e p a s s i v e f i l m i s
n o t r e a d i l y reduced c a t h o d i c a l l y .
Thus, c a t h o d i c
polarization of T i alloys i n neutral chloride solu
t i o n s a r r e s t s c r a c k p r o p a g a t i o n and p r e v e n t s c r a c k
i n i t i a t i o n even though t h e mechanism o f c r a c k i n g i s
t h a t o f hydrogen e m b r i t t l e m e n t . T h i s i s an example i n
+

346
CORROSION
CHEMISTRY
w h i c h t h e r o l e o f t h e p o t e n t i a l on t h e r e p a s s i v a t i o n
p r o c e s s i s more i m p o r t a n t t h e n i t s r o l e on t h e mecha n i s t i c r e a c t i o n o c c u r r i n g on t h e u n f i l m e d m e t a l s u r face.
I n very strong a c i d s o l u t i o n s , i n which t h e
f i l m i s u n s t a b l e and r e p a s s i v a t i o n w i l l n o t t h e r e f o r e
o c c u r , c a t h o d i c p o l a r i z a t i o n has no e f f e c t on c r a c k
v e l o c i t y (2J_, 2) . Where an a c t i v e p a t h mechanism i s
o p e r a t i v e , c a t h o d i c p o l a r i z a t i o n w i l l always lengthen
t f and l o w e r t h e c r a c k v e l o c i t y , e v e n t u a l l y c a u s i n g
crack a r r e s t .
Some a l l o y s e x h i b i t r e v e r s i b l e e m b r i t t l e m e n t ,
e.g., Mg (22), A l (22), T i (24) and Zr (25) a l l o y s .
F o r each a l T o y , e x p e r i m e n t s H v e been done i n w h i c h
specimens were exposed u n s t r e s s e d , t o s o l u t i o n s t h a t
can cause c r a c k i n g , under a v a r i e t y o f c o n d i t i o n s . I f
b r o k e n i n a i r i m m e d i a t e l y a f t e r removal from t h e s o l u t i o n , specimens e x h i b i t e
f
fracture surfaces c h a r a c t e r i s t i
cracking.
I f l a p s e o f t i m e o c c u r s between removal
from s o l u t i o n and s t r e s s i n g , specimens e x h i b i t e d
i n c r e a s e d v a l u e s o f Zf and d e c r e a s e d amounts o f s t r e s s
corrosion-type fracture with increasing length of
lapse o f time.
T h i s b e h a v i o r i s c h a r a c t e r i s t i c o f hydrogen e m b r i t t l e m e n t f r a c t u r e and has been i n t e r p r e t e d as
such f o r t h e f o u r t y p e s o f a l l o y s d e s c r i b e d .
These
are simple b u t very c l e a r experiments.
Preventative
Measures
I t i s c l e a r l y i m p o r t a n t t o know how t o a v o i d , o r
at l e a s t minimize the incidence o f the occurrence o f
such a w i d e s p r e a d t y p e o f f a i l u r e .
The c h o i c e s a r e r e l a t i v e l y few i n number and c a n be c o n v e n i e n t l y c o n s i d e r e d under t h e h e a d i n g s o f t h e words t h a t make up
name o f t h e problem.
S t r e s s . From F i g u r e s 1 and 2 i t has a l r e a d y been
s t a t e d t h a t s t r e s s c o r r o s i o n c r a c k i n g c a n be r e d u c e d
o r a b o l i s h e d a l t o g e t h e r by r e d u c i n g t h e s t r e s s l e v e l ,
d e p e n d i n g upon whether t h e system e x h i b i t s a t h r e s h o l d
stress or value.
I n p r a c t i c e t h i s may mean e n s u r i n g
t h a t components a r e s t r e s s r e l i e f a n n e a l e d , e.g.,
brass tubes a f t e r drawing, o r t h a t welds a r e given
post-weld heat treatements, since i t i s r e s i d u a l
s t r e s s t h a t i s o f t e n t h e p r o b l e m . To m i n i m i z e f a i l u r e s
i n s t e e l tube assemblies h a n d l i n g sour o i l w e l l s , f o r
example, i t i s recommended t h a t a l l w e l d s be k e p t be
low a c e r t a i n h a r d n e s s l e v e l (26). The h a r d n e s s c a n
be measured i n s i t u .
Design can help i n reducing
o p e r a t i n g s t r e s s l e v e l s a l s o . C r i t i c a l f l a w d e p t h has

10.
SCULLY
Stress-Corrosion
Cracking
347
a l s o been m e n t i o n e d . C o n t r o l l i n g f l a w d e p t h i s e a s i e r
t o d e s c r i b e t h e n t o a c h i e v e b u t c a r e s h o u l d be t a k e n
t o p r e v e n t l a r g e f l a w d e p t h s , p a r t i c u l a r l y where a
K
l e v e l exists.
There a r e examples o f t a n k s b e i n g
operated c o n t a i n i n g l i q u i d s t h a t cause s t r e s s c o r r o
s i o n c r a c k i n g w i t h r e s i d u a l and o p e r a t i n g s t r e s s e s
c o n t r o l l e d so t h a t K j
i s n o t exceeded. F o r h i g h
strength a l l o y s overtempering o r overaging w i l l often
g i v e a much more a c c e p t a b l e l i f e t i m e a t t h e c o s t o f a
lower a l l o y s t r e n g t h .
Such c o n s i d e r a t i o n s c a l l f o r a
b a l a n c e between t h e r e q u i r e m e n t s o f t h e p l a n t o p e r a t o r
and t h e demands o f t h e p l a n t d e s i g n e r .
I
Corrosion.
R e d u c i n g c o r r o s i o n by t h e u s e o f i n h i b i t o r s w i l l commonly r e d u c e o r even e l i m i n a t e s t r e s s
c o r r o s i o n c r a c k i n g , p o s s i b l y by moving t h e c o r r o s i o n
p o t e n t i a l outside th
these are r e f e r r e d t
i f t h i s i s t h e i r sole function, cracking w i l l occur
i f t h e c o r r o s i o n p o t e n t i a l moves back i n t o t h e c r a c k
i n g r a n g e . The c o n t r a s t i s made w i t h s a f e i n h i b i t o r s
w h i c h reduce o r p r e v e n t c r a c k i n g even i f t h e c o r r o s i o n
p o t e n t i a l i s i n the c r a c k i n g range. I n p r a c t i c e t h e
use o f i n h i b i t o r s o f e i t h e r c a t e g o r y may be r e s t r i c t e d
by (1) s o l u b i l i t y p r o b l e m s , (2) economic a s p e c t s and
(3) p r a c t i c a l i t y l i m i t s .
Many f a i l u r e s o c c u r i n steam
o r under c o n d e n s a t i o n c o n d i t i o n s .
I n both o f these
cases the t r a n s p o r t o f i n h i b i t o r s t o s i t e s o f crack
i n i t i a t i o n i s n o t f e a s i b l e . W i t h o t h e r s y s t e m s , how
e v e r , q u i t e s m a l l a d d i t i o n s o r changes may e l i m i n a t e
p r o b l e m s , e.g., 1-2% H 0 t o CH3OH/HCI m i x t u r e s , u s i n g
impure 0/| r a t h e r t h a n pure N2O4, b o t h f o r T i a l l o y s .
C a t h o d i c p r o t e c t i o n may a l s o a c h i e v e t h e same e f f e c t
o f a l o w e r e d c o r r o s i o n r a t e . As w i t h i n h i b i t o r s i t s
use i s l i m i t e d and f o r much t h e same r e a s o n s . M e n t i o n
must be made o f c u r r e n t s t r e s s c o r r o s i o n c r a c k i n g
problems i n gas t r u n k t r a n s m i s s i o n l i n e s i n t h e U.S.A.
and e l s e w h e r e . A number o f f a i l u r e s have o c c u r r e d i n
these l i n e s as a r e s u l t o f c e r t a i n carbonate/bicarbo
nate mixtures being generated i n the a l k a l i n e l i q u i d
a d j a c e n t t o t h e p i p e by t h e a p p l i c a t i o n o f c a t h o d i c
p r o t e c t i o n (*0 . T h i s i s i n no way an argument a g a i n s t
the u s e o f s u c h a p r o t e c t i o n method. I t i s m e r e l y a
w a r n i n g about p o s s i b l e e f f e c t s . These f a i l u r e s a l s o
u n d e r l i n e some o f t h e d i f f i c u l t
technical/economic
d e c i s i o n s a t t e n d a n t upon such f a i l u r e s .
There a r e two
q u i t e d i f f e r e n t q u e s t i o n s t o be s e t t l e d :
(1) what c a n
be done t o r e d u c e t h e i n c i d e n c e o f c r a c k i n g i n e x i s t
i n g p i p e l i n e s ? and (2) what c a n be done t o r e d u c e t h e
p o s s i b i l i t y o f c r a c k i n g i n p i p e l i n e s t o be i n s t a l l e d
i n the future?
B o t h t e c h n i c a l l y and e c o n o m i c a l l y t h e
2
American Chemical
Society Library
1155 16th St. N. W.
Washington,
D. C. 20036
348
q u e s t i o n s pose a number o f d i f f e r e n t p r o b l e m s . T h i s i s
i n some ways t y p i c a l o f a l l p r e v e n t a t i v e measures.
There a r e many f a c t o r s t o be c o n s i d e r e d b e f o r e s e t t l i n g
upon an a c c e p t a b l e s o l u t i o n .
The use o f p a i n t i n g s and c o a t i n g s must be ment i o n e d . They a r e u s u a l l y a p p l i e d f o r o t h e r r e a s o n s
t o r e d u c e the r a t e o f g e n e r a l c o r r o s i o n and the c o s t o f
c a t h o d i c p r o t e c t i o n . To the e x t e n t t h e y a r e s u c c e s s f u l ,
they w i l l f r e q u e n t l y minimize the i n c i d e n c e of s t r e s s
c o r r o s i o n f a i l u r e s . C o a t i n g s a l w a y s have f a u l t s i n
them and depending upon c o a t i n g s a l o n e i s u s u a l l y unw i s e . I t i s i n t h e i r use w i t h systems o f c a t h o d i c
p r o t e c t i o n t h a t t h e y a r e t o be j u d g e d , t o g e t h e r w i t h
a b i l i t y t o w i t h s t a n d s e r v i c e c o n d i t i o n s , e.g., c o n t i n ual temperature f l u c t u a t i o n s .
I n c r e a s i n g the c o r r o s i o n r a t e might appear t o be
a rather d r a s t i c counte
sion cracking.
Sinc
c o r r o s i o n , e x t e n d i n g c o r r o s i o n o v e r t h e whole o f the
s u r f a c e w i l l u s u a l l y l e s s e n t h e p r o b a b i l i t y o f such
failures.
T h i s a p p r o a c h i s u n l i k e l y e v e r t o be a
permanent remedy. I t i s employed i n making up m i x t u r e s
c o n t a i n i n g HC1 t o c l e a n a u s t e n i t i c s t a i n l e s s s t e e l
p a r t s i n c h e m i c a l p l a n t : t h e c o r r o s i o n r a t e i s maint a i n e d > 10 mpy
(27).
Cracking.
P o s s i b l e e f f e c t s of plane s t r e s s /
p l a n e s t r a i n t r a n s i t i o n s have a l r e a d y been i n d i c a t e d .
The e f f e c t i v e n e s s o f t h e s t r a i n - r a t e i n p r o m o t i n g
c r a c k i n g can be i m p o r t a n t where e n g i n e e r i n g s t r u c t u r e s
a r e s u b j e c t t o p e r i o d i c s t r a i n i n g , e.g., p i p e l i n e s . I t
i s p o s s i b l e t o have i n t e r r u p t e d l o a d i n g s t r e s s c o r r o s i o n c r a c k i n g i n w h i c h c a s e the s t r e s s combines t o
produce a s t r a i n t r a n s i e n t t h a t g e n e r a t e s a c r a c k
i n c r e m e n t . T h i s i s d i f f e r e n t from c o r r o s i o n f a t i g u e
and t h e i n t e r f a c e between the two has been d i s c u s s e d
(28). I n t e r r u p t e d l o a d i n g s t r e s s c o r r o s i o n c r a c k i n g
can be o f p a r t i c u l a r i m p o r t a n c e where t h e system exh i b i t s a t h r e s h o l d under c o n s t a n t l o a d l a b o r a t o r y
t e s t i n g conditions. A small f l u c t u a t i o n i n load
(1-2%) can reduce t h e t h r e s h o l d by 50% (3).
Unless
laboratory t e s t s simulate accurately service condit i o n s , c o n f u s i o n and a l a c k o f c o n f i d e n c e a r e l i k e l y
t o ensue.
S i n c e a t e n s i l e component o f s t r e s s i s r e q u i r e d ,
s t r e s s c o r r o s i o n c r a c k i n g can be p r e v e n t e d by p u t t i n g
t h e s u r f a c e o f a component i n t o c o m p r e s s i o n , e.g., by
short-peening.
Where t h i s i s p r a c t i c a b l e , i t i s
d e s i r a b l e . The t r e a t m e n t needs t o be a p p l i e d u n i f o r m ly.
I t w i l l n o t be e f f e c t i v e i f p i t t i n g o c c u r s on t h e
compressed l a y e r .

10. SCULLY
Stress-Corrosion Cracking
349
Cracking may be avoided by using a nonsusceptible

or less susceptible alloy. This usually entails using
a more expensive alloy or a greater volume of a lower
strength alloy. From what has been discussed above,
such a choice depends upon a reliable test having been
made in the environment under consideration.
Concluding Remarks
Stress corrosion cracking i s a complicated subject and i t i s necessary to be very careful in making
simplifications. Certain points have been emphasized
in the description presented above. The simple idea of
an imbalance between creep strain-rate and repassivation rate does seem to be an accurate description of
an essential process occurring during the propagation
of a stress corrosio
tleties of this interactio
metallurgical and electrochemical approach. In this
subject a dual approach is always required. To do
accurate tests, potential control is necessary and the
investigation of a range of potentials is always
required. Commercial metallurgical alloys are complicated heterogeneous assemblies of atoms. Some of these
heterogeneities are responsible for cracking.
Some points have been neglected because of the
limitations of space and time. Why is the chloride
ion so prevalent in Table I, for example? The answer
almost certainly lies in i t s effect upon delaying repassivation as a result of metal ion hydrolysis and
the low pH of many metal chlorides. In addition, i t
promotes the i n i t i a l breakdown, probably in much the
same way. With this and other points completely clear
answers and explanations are not yet arrived at.
Progress is being made, however, and eventually a
good i f not perfect, predictive capacity w i l l be
achieved over what remains a facinating and i r r i t a t i n g
phenomenon.
Literature Cited
1.
2.
3.
Staehle, R.W., Forty, A.J. and Van Roogen, D.,

Editors, "Fundemental Aspects of Stress Corrosion Cracking," N.A.C.E., Houston, Texas, 1969.
Scully, J.C., Editor, "The Theory of Stress
Corrosion Cracking in Alloys," N.A.T.O. Brussels,
1971 .
McCright, R.D., Slater, J.E. and Staehle,
R.W.,
Editors, "Stress Corrosion Cracking and Hydrogen
Embrittlement of Iron Base Alloys," N.A.C.E.,

350
CORROSION CHEMISTRY
4.
Swann, P.R., Ford, F.P. and Westwood, A.R.C.,

"Mechanisms of Environment Sensitive Cracking of
Materials," Metals Society, London, 1977.
5.
Brown, B.F., Editor, "Stress Corrosion Cracking in
High Strength Steels and in Titanium and Aluminium
Alloys," N.R.L., Washington, D.C.,
1972.
6.
Engseth, P. and Scully, J.C., Corrosion Science
(1975) 15, 504.
7.
Scully, J.C., Corrosion (1975) 15, 505.
8.
Scully, J.C. and Powell, D.T., Corrosion Science
(1970) 10, 371.
9.
Scully, J.C., Corrosion Science (1975) 15. 207.
10. Scully, J.C., "Stress Corrosion Cracking The
Constant Strain Rate Technique," A.S.T.M.,
Philadelphia, in press.
11. Barbosa, M. and Scully, J.C., "Environment Sensitive Fracture of Engineering Materials," A.I.M.E.
to be published
12. Ambrose, J.R. an Kruger,
,
(1972)
,
30.
13. "Symposium on Stress Corrosion Cracking of Metals,"
A.S.M./A.I.M.E., Philadephia, 1945.
14. Tromans, D. and Nutting, J., Corrosion (1965) 21, 146
15. Swann, P.R., Corrosion (1963) 19, 102.
16. Swann, P.R. and Nutting, J., J. Inst. Met. (1959/
60) 80, 478.
17. Scamans, G. and Swann, P.R., Corrosion Science, in
press.
18. Swann, P.R. and Embury, J.D., "High Strength
Materials," Editor Zackey, V., Wiley, New York,
1965, p. 327.
19. Coleman, E.G., Weinstein, D. and Rostoker, W.,
Acta. Met. (1961) 9, 491.
20. Kermani, M. and Scully, J.C., Corrosion Science,
in press.
21. Powell, D.T. and Scully, J.C., Corrosion (1968) 24,
151.
22. Chakrapani, D.G. and Pugh, E.N., 6th International
Congress on Metallic Corrosion, N.A.C.E., Houston,
to be published.
23. Scamans, G.M., Alani, R. and Swann, P.R., Corrosion science (1976) 16, 443.
24. Adepoju, T. and Scully, J.C., Corrosion Science
(1976) 16, 789.
25. Majumdar, P. and Scully, J.C., Corrosion Science,
in press.
26. N.A.C.E. Standard RP-04-72.
27. Laque, F.L. and Copson, H.R., "The Corrosion Resistance of Metals and Alloys," Reinhold, New York,
1963, p. 392.
28. Parkins, R.N. and Greenwell, B.S., Met. Sci. (1977)
21, 405.
RECEIVED September21,1978.

11
Industrial Problems: Cooling Water and Cooling-Water

Treatment
J. FRED WILKES
Consulting Chemical Engineer, 143 Seventh Avenue, La Grange, IL 60525
The a b i l i t y to dissipate unwanted heat through

cooling systems i s v i t a l to operation of power generating stations and mos
lations.
Open r e c i r c u l a t i n
systems are assuming a steadily increasing proportion
of utility and i n d u s t r i a l cooling loads, as water shortages continue to l i m i t a v a i l a b i l i t y of once-through
cooling water sources.
Cooling water treatment programs all have similar
objectives: 1) to maintain heat transfer e f f i c i e n c y .
2) To preserve operating e f f i c i e n c y of the o v e r a l l
system.
3) To prolong service life of equipment.
Protection of cooling system metals involves complex i n t e r r e l a t e d problems of scale and deposit prevent i o n , c o n t r o l of m i c r o b i o l o g i c a l growths and other
fouling sources, in addition to corrosion mitigation
by i n h i b i t o r s . Corrosion control programs may be expected to vary considerably between systems, since
each i n s t a l l a t i o n presents d i f f e r e n t environmental
factors and operating problems which affect response.
Those of us who own or drive automobiles recognize
the need for cooling systems to remove excess engine
heat and maintain safe operating temperatures.
Industrial
cooling systems must accomplish similar jobs
of heat r e j e c t i o n .
They include many d i f f e r e n t types
and mechanical designs.
In a major refinery or chemical
process p l a n t , r e s i d u a l heat in process f l u i d s and
gases may be employed for generation of high pressure
steam, in heat exchangers of s p e c i a l design c a l l e d
waste heat b o i l e r s .
A waste heat b o i l e r dissipates unwanted process heat while recovering i t s thermal energy
in the form of useful steam.
We l i v e or work in a i r conditioned buildings which
are t o t a l l y enclosed and don't have windows that can be
opened.
Such buildings accumulate heat from humans;
0-8412-0471-3/79/47-089-351$10.00/0

CORROSION
352
CHEMISTRY
from s u n l i g h t ? and from l i g h t i n g systems. T h i s heat

must be d i s p o s e d o f , so t h a t we can l i v e and work i n
c o m f o r t . A i r c o n d i t i o n i n g systems employ m e c h a n i c a l
r e f r i g e r a t i o n u n i t s . The heat d e v e l o p e d i n c o m p r e s s i o n
of r e f r i g e r a n t s used t o remove b u i l d i n g h e a t must be
d i s p o s e d o f by e x t e r n a l means such as c o o l i n g t o w e r s ,
e v a p o r a t i v e c o n d e n s e r s and s p r a y ponds.
Most c o o l i n g towers a r e o p e n - r e c i r c u l a t i n g t y p e s
i n which heat r e j e c t i o n m a i n l y i s a c c o m p l i s h e d by evapor a t i o n o f w a t e r . There a l s o a r e c l o s e d c o o l i n g systems
(of which an a u t o m o b i l e r a d i a t o r would be t y p i c a l ) ,
from which heat i s d i s s i p a t e d by the f o r c e d f l o w o f
air across r a d i a t i o n s e c t i o n s .
I n some c o m b i n a t i o n
s y s t e m s , heat from c l o s e d c o o l i n g c i r c u i t s i s t r a n s f e r red
t h r o u g h heat exchangers i n t o c i r c u l a t i n g water
which i s c o o l e d by e v a p o r a t i v e systems.
Open R e c i r c u l a t i n g C o o l i n
F i g u r e 1 shows a t y p i c a l i n d u c e d d r a f t c o o l i n g
tower o f wood c o n s t r u c t i o n . P o w e r f u l f a n s a t the t o p
draw a i r t h r o u g h l o u v e r s a t the tower base, a c r o s s the
tower f i l l , and d i s c h a r g e i t t h r o u g h f a n s t a c k s . From
d i s t r i b u t i o n t r o u g h s l o c a t e d above the tower f i l l s e c t i o n , incoming hot water from a b u i l d i n g or p l a n t f l o w s
downward over the f i l l ( p a c k i n g ) , p a r t i a l l y e v a p o r a t e s ,
and i s c o o l e d b o t h by e v a p o r a t i o n , c o n v e c t i o n and c o n duction.
F i g u r e 2 i s a s c h e m a t i c o f a n a t u r a l d r a f t , atmos p h e r i c tower. Warm water i s d i s t r i b u t e d a t the t o p ,
and moves down by g r a v i t y a c r o s s wood f i l l .
Air is
drawn i n by chimney e f f e c t . F i g u r e 3 shows a l o n g
bank o f a t m o s p h e r i c t o w e r s , f u n c t i o n i n g l i k e the one
shown i n the s c h e m a t i c . F i g u r e A i l l u s t r a t e s major
c h a r a c t e r i s t i c s o f a c o o l i n g system c o m b i n i n g a c l o s e d
c o o l i n g s e c t i o n w i t h an open ( e v a p o r a t i v e ) c o o l i n g
tower. T h i s d o u b l e r e c i r c u l a t i n g system might be used
to r e j e c t unwanted heat from an i n t e r n a l c o m b u s t i o n
e n g i n e or p r o c e s s u n i t . F i g u r e 5 shows a n o t h e r c o n f i g u r a t i o n o f a d o u b l e r e c i r c u l a t i n g system i n which a
c l o s e d system heat exchanger i n the bottom o f the tower
i s c o o l e d by e v a p o r a t i n g water f l o w i n g down over i t .
Let
us c o n s i d e r how c o o l i n g towers work. What
i s the r e l a t i o n s h i p o f e v a p o r a t i o n t o c o o l i n g tower
o p e r a t i o n ? By c o m p a r i s o n , i n the p r o c e s s o f g e n e r a t i n g
steam, a f t e r h e a t i n g f e e d w a t e r t o i t s b o i l i n g temperat u r e one must add r o u g h l y 1,000 B r i t i s h t h e r m a l u n i t s
(Btu)
o f h e a t energy f o r e v e r y pound o f w a t e r , t o cause
a change o f s t a t e from l i q u i d water t o water vapor
(steam). An e v a p o r a t i v e c o o l i n g system a l s o r e q u i r e s

WILKES
Industrial
Figure 1.
Problems
Cutaway section of induced draft cooling tower

N a t u r a l Draft or C h i m n e y T o w e r
Figure 2.
Schematic of a natural draft cooling tower

Figure 3.
Multicell, natural draft (atmospheric) cooling tower
GO
ce
I*

356
DIE. S C L
PC
ENGINE
CYCUE.
COOLING TOWER
1
CLOSED
^ HEAT
EXCHANGER
WATER
CYCLE.
R E C I R CWLATION
Figure 4.
OIL.
Schematic of a double recirculating cooling system
COOL.K.K
OPftN
D I E S E L E-MGirSEl
PUMP
CYCLE
COOLING
TOWER
Z.
152
RECIRCULATING
CUOStO
Figure 5.
r*UMP
CYCLE
Schematic of a double recirculating cooling system showing heat exchanger

in bottom of cooling tower

11.
WILKES
Industrial
Problems
357
equivalent heat input.

To c a u s e one pound o f w a t e r
t o e v a p o r a t e , we m u s t s u p p l y a b o u t 1 , 0 0 0 B t u o f
heat
e n e r g y f r o m some s o u r c e .
I n a c o o l i n g s y s t e m we t r a n s fer unwanted heat from a p i e c e of equipment i n t o
cooling w a t e r , and cause p a r t of t h a t water to
evaporate.
I n t h e p r o c e s s we w i l l r e j e c t a b o u t 1 , 0 0 0 B t u f o r
every
pound of water caused to e v a p o r a t e .
Practically
speaking,
when h o t w a t e r i s p a s s e d t h r o u g h a c o o l i n g
tower,
a b o u t one p e r c e n t of the w a t e r b e i n g c i r c u l a t e d must
e v a p o r a t e f o r e a c h 10 d e g r e e s F . t e m p e r a t u r e d r o p
accomp l i s h e d i n the tower.
In a c o o l i n g tower c i r c u l a t i n g
2 0 , 0 0 0 g a l l o n s p e r m i n u t e and o p e r a t i n g w i t h 100 d e g r e e s
F . w a t e r c o m i n g i n a t t h e t o p , a n d 80 d e g r e e s F . w a t e r
discharged at the bottom,
( a 20 d e g r e e t e m p e r a t u r e
d r o p ) we w i l l h a v e e v a p o r a t e d 2% o f t h e w a t e r
circulat i n g , at every pass through the
tower.
What s h o u l d happe
a l k a l i n i t y and o t h e
c o o l i n g system and c a u s e d to e v a p o r a t e and
concentrate?
Once t h e l i m i t o f s o l u b i l i t y o f t h e d i s s o l v e d m i n e r a l s
or s a l t s i n that water i s reached, they would begin
t o come o u t o f s o l u t i o n and c r y s t a l l i z e i n s o l i d f o r m .
To t h e e x t e n t t h a t d i s s o l v e d s a l t s i n c l u d e c a l c i u m
and magnesium w h i c h c o u l d combine w i t h s i l i c a ,
sulphate
and c a r b o n a t e , t h e e n d r e s u l t m i g h t be i n s o l u b l e
scale
d e p o s i t s on h e a t t r a n s f e r s u r f a c e s .
We d o n ' t
like
such deposits i n b o i l e r s .
They are e q u a l l y d e s t r u c t i v e i n c o o l i n g system heat e x c h a n g e r s , where
ability
to r e j e c t heat i s e s s e n t i a l to c o n t i n u a t i o n of
process
o p e r a t i o n s , r e f r i g e r a t i o n and a i r c o n d i t i o n i n g s y s t e m s .
S o b y t h e e v a p o r a t i o n o f c o o l i n g w a t e r , we a c c o m p l i s h
the bulk of the i n d u s t r i a l c o o l i n g job.
Such systems
a l s o d i s s i p a t e some h e a t b y r a d i a t i o n a n d c o n v e c t i o n .
But t h e major r e d u c t i o n o f h e a t i s a c c o m p l i s h e d by
evaporation.
A s we e v a p o r a t e a n d c o n c e n t r a t e
cooling
water, d i s s o l v e d m i n e r a l s soon would reach l e v e l s at
which scale d e p o s i t s would form, i n the absence of
c o r r e c t i v e measures.
Calcium carbonate scale
control
is a major
concern.
One way t o p r e v e n t CaCO^ s c a l e i n c o o l i n g
system
exchangers i s to c o n v e r t c a r b o n a t e and b i c a r b o n a t e
i o n s t o some o t h e r f o r m h a v i n g g r e a t e r s o l u b i l i t y i n
heated water.
CaCO-. h a s a v e r y l o w s o l u b i l i t y i n
w a t e r ; n o t m o r e t h a n 20 t o 30 m g / l i t e r .
L i k e most
o t h e r m a t e r i a l s t h a t form s c a l e i n s i t u on heated s u r faces,
i t has a n e g a t i v e s o l u b i l i t y c u r v e ,
(solubility
g o e s down as t e m p e r a t u r e g o e s u p ) .
Other s a l t s
like
sodium c h l o r i d e , sodium carbonate, sodium s u l f a t e
get
more s o l u b l e as t e m p e r a t u r e r i s e s .
Among t h e e a r l y e f f o r t s made t o p r e v e n t CaCO^

358
CORROSION
CHEMISTRY
s c a l i n g and c o r r o s i o n o f c o o l i n g s u r f a c e s and heat

t r a n s f e r u n i t s was a p p l i c a t i o n o f c h e m i c a l e q u i l i b r i u m
p r i n c i p l e s (the C a l c i u m Carbonate S a t u r a t i o n Index)
d e v e l o p e d by W. F. L a n g e l i e r . ( 1 , 2) L a n g e l i e r showed
t h a t each n a t u r a l water s u p p l y would be c o m p l e t e l y
s t a b l e w i t h r e s p e c t t o CaCO^ a t a c e r t a i n pH, which he
i d e n t i f i e d as pH . The water would be e x a c t l y s a t u r a t e d
w i t h c a l c i u m c a r b o n a t e , n e i t h e r u n s a t u r a t e d nor s u p e r s a t u r a t e d . The pH o f a g i v e n water c o u l d be c a l c u l a t e d
from s i m p l e d a t a , I n c l u d i n g c a l c i u m c o n t e n t , t o t a l
a l k a l i n i t y , t e m p e r a t u r e and t o t a l d i s s o l v e d s o l i d s .
S i m p l e c h a r t s and nomographs were d e v e l o p e d t o s i m p l i f y
d e t e r m i n a t i o n o f pH . L a n g e l i e r a l s o proposed the
S a t u r a t i o n Index, t o show whether a water s u p p l y would
be s t a b l e or u n s t a b l e ( w i t h r e s p e c t t o CaCO^ s o l u b i l i t y )
at any g i v e n t e m p e r a t u r e and pH
Having d e t e r m i n e
g r a p h s or c a l c u l a t i o n s
a c t u a l pH o f the w a t e r . S u b t r a c t pH
from the a c t u a l
pH; i f the r e s u l t i s a p o s i t i v e number t h i s i n d i c a t e s
a s c a l i n g w a t e r , w i t h more c a l c i u m c a r b o n a t e i n s o l u t i o n
than can be h e l d . The h i g h e r the p o s i t i v e s a t u r a t i o n
index r i s e s , the g r e a t e r w i l l be the s c a l i n g tendency.
What i f the S a t u r a t i o n Index, (pH - p H ) , i s a n e g a t i v e
number? T h i s i n d i c a t e s a water t h a t i s u n d e r s a t u r a t e d
w i t h c a l c i u m c a r b o n a t e , and hungry t o d i s s o l v e more.
I f t h e r e , i s no c a l c i u m c a r b o n a t e handy t o be d i s s o l v e d ,
the water w i l l a t t a c k the m e t a l s o f the system. I n
o t h e r words, a n e g a t i v e pH
i n d i c a t e s a c o r r o s i v e water.
The more n e g a t i v e the S a t u r a t i o n Index, the more c o r r o s i v e the water w i l l be.
John Ryznar o f NALCO d e v e l o p e d a u s e f u l m o d i f i c a t i o n c a l l e d the S t a b i l i t y Index, based on e m p i r i c a l
d a t a from f i e l d l o c a t i o n s . The S a t u r a t i o n pH i s d e t e r mined e x a c t l y the same way, but the Index i s o b t a i n e d
d i f f e r e n t l y . The S t a b i l i t y Index i s c a l c u l a t e d from
(2 p H - pH).
I t always w i l l be a p o s i t i v e whole number.
S t a b i l i t y Index numbers around 7 show the water
i s q u i t e s t a b l e , n e i t h e r c o r r o s i v e nor s c a l i n g .
As
the S t a b i l i t y Index d r o p s below 6, water becomes p r o g r e s s i v e l y more s c a l i n g . On the o t h e r hand, as the
S t a b i l i t y Index r i s e s above 7, water becomes p r o g r e s s i v e l y more c o r r o s i v e . A c o o l i n g water w i t h a S t a b i l i t y
Index o f 10 might produce s e v e r e t o i n t o l e r a b l e c o r r o sion conditions.
Some p i o n e e r s i n c o o l i n g system water t r e a t m e n t
a t t e m p t e d t o c o n t r o l c o r r o s i o n by S a t u r a t i o n Index adjustments alone, without a d d i t i o n of chemical i n h i b i t ors.
U n f o r t u n a t e l y , most c o o l i n g systems i n c l u d e heat
e x c h a n g e r s w i t h wide t e m p e r a t u r e v a r i a t i o n s . A c o o l i n g
g

11.
WILKES
Industrial
Problems
359
w a t e r c o m p l e t e l y s t a b l e a n d n o n - c o r r o s i v e a t 70 d e g r e e s
F . m i g h t become e i t h e r s c a l i n g or c o r r o s i v e , when p a s s ed t h r o u g h an e x c h a n g e r where t e m p e r a t u r e was r a i s e d t o
130 d e g r e e s F .
T h e r e f o r e , c o r r o s i o n c o n t r o l by S a t u r a t i o n Index adjustment alone r a r e l y o f f e r e d a p r a c t i c a l
solution.
The n e x t a p p r o a c h t o s c a l e c o n t r o l was r e d u c t i o n
o f p o t e n t i a l c a l c i u m c a r b o n a t e by a c i d i f i c a t i o n o f
makeup w a t e r .
S u l f u r i c a c i d i s added to reduce
alkal i n i t y and c o n v e r t most of the c a l c i u m b i c a r b o n a t e
to calcium s u l f a t e .
C a l c i u m s u l f a t e i s s o l u b l e up
to about 1,700 p a r t s per m i l l i o n i n c o o l i n g w a t e r s a t
o r d i n a r y temperatures, whereas c a l c i u m carbonate
solub i l i t y i s l e s s t h a n 30 p p m .
So by s l i g h t l y a c i d i f y i n g
m a k e u p w a t e r we g r e a t l y r e d u c e t e n d e n c y f o r c a l c i u m
carbonate deposition.
The c a l c i u m s u l f a t e l e v e l i n
concentrated cooling
adjustmentmanually
O b v i o u s l y w h e n we d e l i b e r a t e l y a d d s u l f u r i c a c i d
t o c o o l i n g w a t e r , we r e d u c e a l k a l i n i t y a n d a l s o d e p r e s s
pH.
T h i s increases c o r r o s i v i t y of the c i r c u l a t i n g
water, which i s saturated with dissolved oxygen,
cont a c t s many d i s s i m i l a r m e t a l s , a n d i s e l e v a t e d i n t e m p e r ature.
In the process of a c i d i f i c a t i o n to prevent
s c a l e d e p o s i t i o n so heat t r a n s f e r equipment w i l l
funct i o n e f f i c i e n t l y , we k n o w i n g l y b u i l d i n a d d e d
corrosion
f a c t o r s and i n c r e a s e c o r r o s i o n c o n t r o l d i f f i c u l t y .
Now
we n e e d t o f i n d c o r r o s i o n i n h i b i t o r c o m b i n a t i o n s w h i c h
w i l l be p r a c t i c a l f o r use i n i n d u s t r i a l s y s t e m s ;
can
be t o l e r a t e d f r o m t h e v i e w p o i n t s o f t o x i c i t y and p o l l u t i o n c o n t r o l s and w i l l e f f e c t i v e l y p r o t e c t these
multim e t a l c i r c u i t s d u r i n g t h e i r n o r m a l s e r v i c e l i f e o f 20 t o
30 y e a r s .
One e a r l y a p p r o a c h f o r c o o l i n g w a t e r c o r r o s i o n i n h i b i t i o n was t h e u s e o f i n o r g a n i c p o l y p h o s p h a t e s .
These
c o m p l e x m o l e c u l a r l y d e h y d r a t e d p h o s p h a t e s came i n t o
widespread i n d u s t r i a l use b e g i n n i n g i n the
1930's.
T h e r e i s some d i s a g r e e m e n t a b o u t how p o l y p h o s p h a t e s
f u n c t i o n as c o r r o s i o n i n h i b i t o r s .
Generally accepted
t h e o r y i s t h a t , i n an a e r a t e d s y s t e m , they cause f o r m a t i o n of a p r o t e c t i v e surface f i l m which contains both
i r o n o x i d e and p h o s p h o r u s , perhaps an i r o n
phosphate.
P o l y p h o s p h a t e s w i l l not work i n a system t h a t i s d e v o i d
of oxygen, nor i n a stagnant system.
Polyphosphate corr o s i o n i n h i b i t i o n required flow, to replace the
ironphosphate f i l m as f a s t as i t i s removed or
depleted.
P o l y p h o s p h a t e s are u n s t a b l e and s u b j e c t to problems i n
h i g h t e m p e r a t u r e c i r c u i t s , o r where pH f l u c t u a t i o n
occurs.
E c o l o g i c a l considerations also are involved,
because of p o s s i b l e p o l l u t i o n c o n t r i b u t i o n s of r e s i d u a l

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phosphates i n c o o l i n g tower d i s c h a r g e s to
surface
waterslakes, streams,
etc.
In the e a r l y 1950's, combinations of a l k a l i
chromate (an a n o d i c i n h i b i t o r ) and p o l y p h o s p h a t e
(generally
a c c e p t e d as c a t h o d i c )
came i n t o p r o m i n e n c e f o r
cooling
system c o r r o s i o n i n h i b i t i o n .
The c o m b i n a t i o n o f
chromate w i t h phosphates proved h i g h l y e f f i c i e n t i n c o m p a r i son w i t h s t r a i g h t phosphate or s t r a i g h t chromate, and
c o u l d be u s e d a t s u b s t a n t i a l l y l o w e r
concentrations.
For example, a c o o l i n g system t h a t had been t r e a t e d
w i t h 4 0 0 ppm a l k a l i c h r o m a t e , w i t h c o o l i n g w a t e r p H
a d j u s t e d t o t h e n e u t r a l r a n g e o f pH 7 t o 8, c o u l d be
e q u a l l y w e l l p r o t e c t e d by a c o m b i n a t i o n o f c h r o m a t e and
p o l y p h o s p h a t e , w i t h c h r o m a t e c o n c e n t r a t i o n o f 30 t o 40
p p m , a n d p h o s p h a t e a t 10 t o 20 p p m .
In the l a t e 1950's, chromate-phosphate
systems
incorporating zinc a
introduced, followe
out phosphate.
Using c h r o m a t e - z i n c , or
polyphosphatec h r o m a t e - z i n c i n h i b i t o r s i t was p o s s i b l e t o c u t w o r k i n g
concentrations s t i l l further.
I t was n e c e s s a r y
to
c o n t r o l pH t o make t h i s i n h i b i t o r s y s t e m f u n c t i o n
effectively.
A t i n c r e a s e d pH ( a b o v e pH 7 . 5 ) t e n d e n c y
for
z i n c l o s s by p r e c i p i t a t i o n i n c r e a s e s .
F u r t h e r m o r e , pH
r i s e may c a u s e h e a t e x c h a n g e r s t o b e c o m e f o u l e d by z i n c
hydroxide s l i m e s or z i n c phosphate.
We h a v e m e n t i o n e d r e l a t i o n s h i p o f s c a l i n g a n d d e p o s i t i o n to corrosion c o n t r o l .
When c o n s i d e r i n g
deposit i o n causes, we're concerned not only with calcium c a r bonate and c a l c i u m p h o s p h a t e , but a l s o w i t h d u s t and
o t h e r i m p u r i t i e s . The c o o l i n g tower a c t s as an e f f i c i e n t
s c r u b b e r for such s o l i d s , and f o r c o m b u s t i o n gases
such as s u l p h u r d i o x i d e which are p o t e n t r e d u c i n g
agents
for chromtes.
We m u s t a l s o c o n s i d e r
microbiological
g r o w t h s w h i c h form s l i m y d e p o s i t s and i n t e r f e r e w i t h
heat t r a n s f e r .
I n s h o r t , we m u s t b e c o n c e r n e d
about
a l l causes of f o u l i n g i n c l u d i n g d e p o s i t i o n of i n h i b i t o r
r e a c t i o n p r o d u c t s , p r o c e s s l e a k a g e s and c o r r o s i o n
products.
A l l o f t h e p r e c e d i n g i m p u r i t i e s m u s t be d e a l t
w i t h e f f e c t i v e l y so t h a t c o o l i n g water c o r r o s i o n
inhibitors can f u n c t i o n .
Unless the metal surfaces i n the
system are kept c l e a n and a c c e s s i b l e to the
inhibitor,
t h e n t h e c o r r o s i o n i n h i b i t o r c a n n o t be e x p e c t e d
to
function.
I f we p e r m i t g r o w t h o f m i c r o b i o l o g i c a l l a y e r s
on a s u r f a c e , both heat t r a n s f e r and c o r r o s i o n
inhibition will
suffer.
The need t o keep m e t a l s u r f a c e s c l e a n l e d t o the
development of a d d i t i v e s c a l l e d a n t i f o u l a n t s and d i s persants.
Many n a t u r a l o r g a n i c s s u c h as t a n n i n s and
l i g n i n d e r i v a t i v e s have been used as d i s p e r s a n t s .
As an

11.
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Industrial
Problems
361
o u t g r o w t h o f work o r i g i n a t e d i n the b o i l e r water chemist r y f i e l d , i t became a p p a r e n t t h a t s y n t h e t i c compounds

based on a c r y l i c or m e t h a c r y l i c a c i d a l s o were u s e f u l
as a n t i f o u l a n t s i n c o o l i n g c i r c u i t s .
(3, 4, 5, 6)
They
a i d i n d i s p e r s i o n of s i l t , c o r r o s i o n p r o d u c t s , r e s i d u e s
from b a c t e r i a l growth and o t h e r f o u l a n t s . Other s y n t h e t i c d i s p e r s a n t - a n t i f o u l a n t s i n c l u d e phosphated p o l y a l c o h o l s . A v a r i e t y of c h e l a n t / s e q u e s t r a n t s a l s o have been
used, p a r t i c u l a r l y p h o s p h o n i c a c i d d e r i v a t i v e s h a v i n g
s t r u c t u r e s analogous t o the n i t r o g e n - b a s e d c h e l a n t s EDTA
and NTA.
In p r a c t i c e the l a t e r c h e l a n t s are r a r e l y used
because of t h e i r tendency t o complex and remove p r o t e c t i v e o x i d e l a y e r s from heat exchanger s u r f a c e s , p a r t i c u l a r l y a t lower pH l e v e l s commonly m a i n t a i n e d i n c o o l i n g
water.
E a r l i e r the s t a n d a r d i n d u s t r i a l approach t o p r e v e n t i o n of calcium carbonat
f u r i c a c i d was d e s c r i b e d
bicarbonate a l k a l i n i t y , convert calcium carbonate to
c a l c i u m s u l f a t e , and r e g u l a t e s u l f a t e c o n c e n t r a t i o n by
b l e e d o f f . C o r r o s i o n i n h i b i t o r s were added t o p r o t e c t
system m e t a l s . A new approach t o i n d u s t r i a l c o o l i n g
system t r e a t m e n t does not r e q u i r e a d d i t i o n o f s u l f u r i c
acid.
I t i n v o l v e s a p p l i c a t i o n o f phosphonate squest r a n t s , d i s p e r s a n t s and s p e c i a l c o r r o s i o n i n h i b i t o r s ,
and p r o v i d e s d e p o s i t c o n t r o l e q u a l t o t h a t o b t a i n a b l e
when u s i n g s u l f u r i c a c i d . A v a i l a b i l i t y o f phosphonate
squestrants makes p o s s i b l e c o m b i n a t i o n s c a l e c o n t r o l
and c o r r o s i o n i n h i b i t o r s t h a t can be used w i t h o u t the
n e c e s s i t y o f r e d u c i n g c o o l i n g water a l k a l i n i t y by a c i d
feed.
A l k a l i n i t y and c a l c i u m h a r d n e s s o f c i r c u l a t i n g
water b u i l d up t o a l e v e l d e t e r m i n e d by a l l o w a b l e o p e r a ting concentrations.
System pH u s u a l l y p l a t e a u s i n the
s t a b i l i z a t i o n range o f pH8 t o 9.
So l o n g as the Langel i e r S a t u r a t i o n Index of c o n c e n t r a t e d c o o l i n g water
can be kept below +2.0 by b l e e d o f f , s u p p l e m e n t a l a c i d
f e e d i s not r e q u i r e d f o r s c a l e c o n t r o l .
For many l o c a t i o n s , the p h o s p h o n a t e / d i s p e r s a n t
combination provides e f f e c t i v e scale c o n t r o l without
n e c e s s i t y of a c i d i f i c a t i o n .
How does t h i s type o f
t r e a t m e n t f u n c t i o n as a c o r r o s i o n i n h i b i t o r ? One poss i b l e explanation i s that i f a surface i s clean, free
from d e p o s i t s of any type t h a t can s e t up l o c a l c o n c e n t r a t i o n c e l l s , then any c o r r o s i o n o c c u r r i n g w i l l be
u n i f o r m l y d i s t r i b u t e d and reduced i n s e v e r i t y . T h i s
p e r m i t s normal s e r v i c e l i f e o f system equipment.
This
approach t o c o r r o s i o n c o n t r o l i s c a l l e d the " c l e a n
system c o n c e p t . " Copper i n h i b i t o r s ( t h i a z o l e s and
t r i a z o l e s ) f u n c t i o n w e l l i n these combinations.
Addi-

CORROSION
362
CHEMISTRY
t i o n a l c o r r o s i o n s u p p r e s s i o n i s p r o v i d e d by i n c r e a s e d
a l k a l i n i t y and pH i n n o n - a c i d i f i e d systems, p l u s i n h i b i t o r p r o p e r t i e s o f the phosphonate squestrants. I t has
a l s o been d i s c o v e r e d t h a t o t h e r i n h i b i t o r s such as
chromate can be used i n c o m b i n a t i o n w i t h s p e c i a l l y
s e l e c t e d squestrants t o o b t a i n improved c o r r o s i o n
inhibition.
T h i s p r e s e n t a t i o n w i l l not attempt d e t a i l e d d i s c u s s i o n o f m i c r o b i c i d e s , which a r e e s s e n t i a l t o maintenance
o f c l e a n m e t a l s u r f a c e s needed f o r e f f e c t i v e c o r r o s i o n
i n h i b i t i o n . A l l o f the p r e v i o u s l y d i s c u s s e d needs a l s o
must be met, i n c l u d i n g d e p o s i t c o n t r o l , a n t i f o u l a n t s t o
p r e v e n t l o c a l i z e d a c c u m u l a t i o n s o f suspended, i n s o l u b l e
c o n t a m i n a n t s , and a d d i t i o n o f c o r r o s i o n i n h i b i t o r s .
The
c o n t r i b u t i o n s o f m i c r o b i i c i d e s and a s s o c i a t e d a n t i f o u l a n t s
to c o r r o s i o n p r e v e n t i o n i n c o o l i n g systems cannot be
m i n i m i z e d . We a r e c o n c e r n e
b i o l o g i c a l growths ( a l g a
l y and i n t e r f e r e w i t h u n i f o r m water d i s t r i b u t i o n t h r o u g h
the tower, but a l s o w i t h s l i m e f o r m e r s t h a t d e p o s i t i n s i d e heat exchanger t u b e s , and which reduce e f f i c i e n c y
o f h e a t t r a n s f e r j u s t as would s c a l e d e p o s i t s . B i o c i d e s
a l s o p l a y a key r o l e i n p r o t e c t i o n o f wood s t r u c t u r a l
members and wood f i l l s e c t i o n s a g a i n s t d e s t r u c t i o n by
r o t or f u n g a l m i c r o o r g a n i s m s .
The way i n which a q u a t i c growths and m i c r o o r g a n i s m s
can i n t e r f e r e w i t h u n i f o r m c i r c u l a t i o n , or s c r e e n o f f
p a r t o f heat exchange s u r f a c e s from u n i f o r m c o n t a c t w i t h
c o o l i n g water and c o r r o s i o n i n h i b i t o r s can be v i s u a l i z e d
from F i g u r e 6. T h i s shows a s i z e a b l e a c c u m u l a t i o n o f
a q u a t i c weeds on the i n l e t t o a l a r g e heat exchanger.
Some tubes a r e t o t a l l y b l o c k e d .
A c t i v e c o r r o s i o n may be
e x p e c t e d beneath d e p o s i t s where m e t a l s u r f a c e s a r e
s c r e e n e d from f r e e c o n t a c t w i t h i n h i b i t e d c o o l i n g w a t e r .
C l o s e d R e c i r c u l a t i n g C o o l i n g Systems
I n open r e c i r c u l a t i n g systems e v a p o r a t i o n i s the
major f a c t o r i n heat d i s p o s a l . I n t h e s e e v a p o r a t i v e
systems c i r c u l a t i n g water i s c o n t i n u o u s l y scrubbed w i t h
a i r , t h e r e f o r e s a t u r a t e d w i t h d i s s o l v e d oxygen.
In
c o n t r a s t , water i n c l o s e d r e c i r c u l a t i n g c o o l i n g systems
u s u a l l y w i l l c o n t a i n minimum d i s s o l v e d oxygen, even
though the systems may i n c l u d e v e n t e d e x p a n s i o n t a n k s .
C l o s e d c o o l i n g svstems o p e r a t e a t a p p r e c i a b l e p r e s s u r e , o f t e n 30 pounds per square i n c h or h i g h e r .
They
are e s s e n t i a l f o r t e m p e r a t u r e c o n t r o l o f i n t e r n a l comb u s t i o n e n g i n e s used i n a u t o m o b i l e s , t r a c t o r s , t r u c k s ,
buses and r a i l w a y l o c o m o t i v e s .
D i e s e l engines a l s o
p r o v i d e m o t i v e power f o r r i v e r and l a k e v e s s e l s and a r e

WILKES
Figure 6.
Industrial
Problems
363
Cooling system heat exchanger partly clogged by aquatic weeds and

shellfish

364
CORROSION
CHEMISTRY
used t o d r i v e e l e c t r i c g e n e r a t o r s i n power p l a n t s , b o t h
f o r f u l l time and emergency stand-by u s e .
I n t y p i c a l r a i l w a y d i e s e l e n g i n e s , c o o l i n g water
i s pumped t h r o u g h water j a c k e t s o r c o r e d l i n e r s i n
which t h e p i s t o n s work. I t then p a s s e s t h r o u g h t h e
c y l i n d e r heads which must d i s s i p a t e tremendous heat
c r e a t e d by c o m b u s t i o n o f d i e s e l f u e l under p r e s s u r e ;
f i n a l l y i t r e t u r n s t o an e x p a n s i o n tank v i a f a n - c o o l e d
r a d i a t o r s e c t i o n s . A p a r a l l e l c o o l i n g flow passes
t h r o u g h l u b r i c a t i n g o i l heat exchangers t o remove a d d i t i o n a l heat.
In the design o f r a i l w a y D i e s e l engines the b u i l d e r s a p p a r e n t l y , d i d n o t r e c o g n i z e t h a t t h e r e c o u l d be
c o r r o s i o n problems w i t h i n t h e c o o l i n g c i r c u i t s .
This
may e x p l a i n why some c o o l i n g systems i n c l u d e d as many
as t w e l v e d i s s i m i l a r m e t a l s , a l l e l e c t r i c a l l y c o u p l e d
t o g e t h e r . M e t a l s use
b r a s s , A d m i r a l t y , phospho
c a s t and wrought aluminum, t i n - p l a t e d A d m i r a l t y , s o l d e r
and o t h e r s i n a v a r i e t y o f dangerous c o u p l e s .
The r a i l r o a d s were t o l d by l o c o m o t i v e b u i l d e r s t h a t
when they bought D i e s e l s t o r e p l a c e steam l o c o m o t i v e s ,
they c o u l d f o r g e t about water p r o b l e m s ,
unfortunately
the d e s i g n e r s were n o t c o r r o s i o n e n g i n e e r s , and d i d n ' t
d e s i g n c o o l i n g systems t o w i t h s t a n d c o n t i n u o u s c o n t a c t
w i t h h i g h t e m p e r a t u r e c o o l i n g w a t e r . There was an
added need f o r b o i l e r f e e d w a t e r , s i n c e D i e s e l - p o w e r e d
t r a i n s s t i l l r e q u i r e d steam f o r h e a t i n g c a r s , f o r l a v a t o r i e s and f o r d i n i n g c a r s . T h i s r e q u i r e d compact steam
g e n e r a t o r s o f u n i q u e d e s i g n , s m a l l enough t o be i n s t a l l e d aboard D i e s e l l o c o m o t i v e s , y e t c a p a b l e o f g e n e r a t i n g
3 , 0 0 0 - 5 , 0 0 0 l b s . steam/hour.
These b o i l e r s r e q u i r e d
m i n e r a l - f r e e feedwater supplemented by c o r r o s i o n i n h i b i t o r s . C o o l i n g systems a l s o needed h i g h - q u a l i t y makeup
water, p l u s s p e c i a l c o r r o s i o n i n h i b i t o r s t o p r o t e c t the
multimetal c i r c u i t s .
A t some l o c a t i o n s where D i e s e l e n g i n e s were used t o
d r i v e e l e c t r i c g e n e r a t o r s , a t t e m p t s were made t o r e c o v e r
p a r t o f t h e heat i n r e c i r c u l a t i n g c o o l i n g w a t e r . E n g i n e
c o o l a n t c i r c u l a t i n g a t 3 0 pounds p r e s s u r e and temperat u r e s o f 2 4 0 t o 2 5 0 d e g r e e s F. was a l l o w e d t o pass
t h r o u g h an o r i f i c e i n t o an e x p a n s i o n chamber. P a r t o f
the water would f l a s h i n t o low p r e s s u r e steam, which
c o u l d be used f o r b u i l d i n g h e a t i n g . T h e o r e t i c a l l y , a l l
t h e steam condensed i n space h e a t e r s and r a d i a t o r s
would be r e c o v e r e d as c o n d e n s a t e and r e t u r n e d t o t h e
e n g i n e c o o l i n g system. U n f o r t u n a t e l y , h e a t i n g systems
a r e never c o m p l e t e l y t i g h t , so l o s s e s o f steam and c o n d e n s a t e o c c u r r e d . T h i s c r e a t e d a need f o r c o n t i n u o u s
makeup t o t h e c o o l i n g s y s t e m w h i c h i n e f f e c t had become

11.
WILKES
Industrial
Problems
365
a steam g e n e r a t o r .
S i n c e i t was o p e r a t i n g as a s t e a m
generator,
t h e c o o l i n g s y s t e m now r e q u i r e d b l o w d o w n
(to c o n t r o l b u i l d - u p of d i s s o l v e d s o l i d s ) , p l u s v o l a t i l e
c o r r o s i o n i n h i b i t o r s capable of p r o t e c t i n g
steam-condens i n g and condensate
r e t u r n c i r c u i t s p l u s the i n h i b i t o r s
a l r e a d y needed for c o o l i n g system c o r r o s i o n
control.
Most i n t e r n a l combusion engines include
fan-cooled
radiators in their cooling circuits.
Figure 7 is part
of a t y p i c a l r a d i a t o r s e c t i o n .
The c o m p l e t e
radiator
s e c t i o n had 212 r e c t a n g u l a r t u b e s a b o u t one i n c h by
1/8
i n c h i n s i d e d i a m e t e r , w i t h tube metal t h i c k n e s s
about 0.005 i n c h .
The t u b e m e t a l g e n e r a l l y was A d m i r a l t y b r a s s , a 7 0 / 3 0 b r a s s w i t h 1% t i n .
The header a l s o
is
A d m i r a l t y , c o v e r e d w i t h a 1/8
inch l a y e r 60/40 l e a d - t i n
solder.
The t u b e s f i r s t a r e l o c k e d i n p l a c e w i t h
90/10
solder before a p p l y i n g the s e a l i n g l a y e r of 60/40
solder.
The r a d i a t o r t u b e
tin plated.
This combinatio
rosion couple of A d m i r a l t y brass with t i n p l a t i n g i n
c o m b i n a t i o n w i t h two s o l d e r s and s u b j e c t t o
intense
s t r e s s e s i n the header
areas.
Some d i e s e l l o c o m o t i v e s m u s t w o r k u n d e r
extreme
c o l d weather c o n d i t i o n s with a l t e r n a t e periods of
idling
and maximum l o a d i n g .
T h i s can c r e a t e extrenie r a d i a t o r
stresses which contribute to c o r r o s i o n .
One s u c h
locat i o n i s deep p i t open c u t i r o n mines of N o r t h e r n M i n n e sota.
When e n g i n e s w e r e i d l i n g , r a d i a t o r s e c t i o n s
were
bypassed and would r e a c h ambient t e m p e r a t u r e , as low as
-40 degrees F .
U n d e r h e a v y l o a d , r a d i a t o r s w o u l d be
h i t by sudden f l o w s of c o o l i n g w a t e r a t
temperatures
of 220-240 degrees F .
The r e s u l t i n g s t r e s s l o a d s
created c o r r o s i o n f a i l u r e s of the t i n - c o a t e d
tube-solder
j o i n t at the header.
Water l e a k s and r a d i a t o r f a i l u r e s
resulted.
F i g u r e 8 i s a c l o s e u p o f one t u b e end from
a failed radiator section.
I n d i c a t i o n s of
separation
o f t h e t u b e f r o m i t s s u r r o u n d i n g s o l d e r l a y e r c a n be
seen a t the r i g h t and l e f t tube
sides.
Many y e a r s a g o , c e r t a i n A r c t i c e x p l o r e r s c a r r i e d
food i n cans sealed with pure t i n s o l d e r .
Under A r c t i c
t e m p e r a t u r e s t h i s t i n s o l d e r bond f a i l e d
completely.
A p p a r e n t l y the t i n changed from a c r y s t a l l i n e form to
an amorphous, powdered s o l i d which d e s t r o y e d the s e a l
integrity.
R e s u l t i n g f o o d s p o i l a g e c a u s e d d e a t h s by
poisoning.
T h i s type c o r r o s i o n f a i l u r e of pure t i n ,
c a l l e d " t i n p e s t , " or " t i n d i s e a s e , " a l s o had been
o b s e r v e d many y e a r s a g o i n R u s s i a .
Russian cathedrals
u s u a l l y were not h e a t e d , and i n the w i n t e r would r e a c h
extremely low temperatures.
P i p e o r g a n s i n some c a t h e d r a l s h a d p i p e s made o f p u r e b l o c k t i n .
Under extreme
c o l d t e m p e r a t u r e s v i b r a t i n g o r g a n p i p e s were known

366
Figure 7.
Typical air-cooled radiator section for closed-engine cooling system

WILKES
Figure 8.
Industrial
Problems
367
Top of individual tube, closed-system radiator section, where solder

failure caused leakage

CORROSION
368
CHEMISTRY
to
develop areas of " t i n p e s t " and f a i l m e c h a n i c a l l y .

Under extreme low temperature o p e r a t i o n s of D i e s e l
e n g i n e s t h e r a d i a t o r f a i l u r e s o c c u r r i n g seemed t o i n volve very similar corrosion reactions.
Apparently the
t i n l a y e r on the tube s u r f a c e c o n v e r t e d to an amorphous,
powder f o r m , b r e a k i n g the bond between t u b e , s o l d e r and
header.
F i g u r e 8 a l s o shows e v i d e n c e o f s u r f a c e
attack
on t h e s o l d e r l a y e r , by c o n v e r s i o n o f t i n t o
amorphous
form.
The c o r r o s i o n i n h i b i t o r used i n t h e s e
systems
was a b o r a t e - n i t r i t e - m e r c a p t o b e n z o t h i a z o l e p r o p r i e t a r y
composition.
Clean r a d i a t o r tubes are r e a d i l y protected
by
c o n v e n t i o n a l a l k a l i n e chromate or b o r a t e - n i t r i t e c o r r o sion inhibitors in cooling water.
Partially
clogged
t u b e s , however, c r e a t e both heat t r a n s f e r and c o r r o s i o n
problems.
F i g u r e 9 s h o w s a r a d i a t o r s e c t i o n w i t h 90%
of the tubes p a r t l y
s i l t and o i l y p a r t i c u l a t
f l o w s o f a b o u t 250 gpm, t h e s e c t i o n ' s 212 t u b e s
each
s h o u l d c o n d u c t about 1 gpm, c o r r e s p o n d i n g w i t h a f l o w
v e l o c i t y of 4-5 f t . / s e c .
I f 40% o f t u b e s a r e
clogged,
f l o w v e l o c i t y i n r e m a i n i n g o p e n t u b e s may a p p r o a c h 15
t o 20 f t . / s e c .
From p r a c t i c a l e x p e r i e n c e and r e s e a r c h ,
the upper l i m i t s of flow v e l o c i t y for A d m i r a l t y brass
t u b e s a r e i n t h e r a n g e o f 5-7 f t . / s e c .
With higher
flow
v e l o c i i e s , they are subject to impingement f a i l u r e s .
Impingement A t t a c k .
T h i s i s an e l e c t r o c h e m i c a l
phenomenon i n w h i c h p a r t of the s u r f a c e o x i d e i s removed
loc a l l y , l e a v i n g bare m e t a l which becomes a n o d i c .
Metal
l o s s b e g i n s a t a n o d i c s p o t s ; as the p i t deepens, c a v i t a t i o n and s c o u r i n g take o v e r .
The p i t s tend t o u n d e r c u t
in the d i r e c t i o n of flow.
L o o k i n g down f r o m t h e
top
they look l i k e hoof t r a c k s g o i n g i n an upstream d i r e c tion.
As u n d e r c u t t i n g areas e n l a r g e , s m a l l p i e c e s
b r e a k away t o p r o d u c e l a r g e h o l e s o r p e n e t r a t i o n
f a i l ures.
L o o k i n g down i n t o t u b e s w h e r e i m p i n g e m e n t
f a i l u r e s have o c c u r r e d , one c a n see b r i g h t s p o t s t h a t l o o k
like tiny drilled
holes.
How m u c h c o o l i n g w o u l d o n e e x p e c t t o a c c o m p l i s h i n
t h e h e a t e x c h a n g e r shown i n F i g u r e 10?
T h i s i s the
r e s u l t o b t a i n e d when u s i n g d i r t y makeup w a t e r w i t h
s i l t
and c o r r o s i o n p r o d u c t s , w i t h no p r e v e n t i v e m a i n t e n a n c e .
C o o l i n g s y s t e m s m u s t be d e s i g n e d t o p e r m i t m e c h a n i c a l
c l e a n i n g and o t h e r p r e v e n t i v e m a i n t e n a n c e , or
effective
c o r r o s i o n c o n t r o l becomes i m p o s s i b l e .
Concentration Cells.
a r e common i n c l o s e d
r i v e t e d t o g e t h e r , as
L o c a t i o n s encouraging such attack

cooling systems.
Consider metals
in Figure 11.
In the
crevice,

WILKES
Figure 9.
Industrial
Problems
High coolant velocities in unclogged tubes of radiator section caused

impingement attack and penetrating failures.

369
370
Figure 10.
Poorly maintained heat exchanger; water passages clogged by silt,

corrosion products, and other insoluble impurities

11.
WILKES
Industrial
371
Problems
c o o l i n g water would have a s l i g h t l y lower oxygen c o n

t e n t . C o r r o s i o n o c c u r s i n the low oxygen s p a c e , the
l o c u s o f c o r r o s i o n i n an oxygen c o n c e n t r a t i o n c e l l .
In
c o n t r a s t , i n a somewhat s i m i l a r c o n s t r u c t i o n , c o r r o s i o n
may be i n t e n s i f i e d a t the open end o f a c r e v i c e , away
from the a r e a o f h i g h m e t a l i o n c o n c e n t r a t i o n .
The
c o r r o s i o n c u r r e n t f l o w s from the m e t a l towards the low
m e t a l i o n c o n c e n t r a t i o n as shown i n F i g u r e 12^
In
c o o l i n g systems many components a r e p o o r l y d e s i g n e d
to prevent c r e v i c e c o r r o s i o n .
An example o f c o n c e n t r a t i o n c e l l c o r r o s i o n i s shown
i n F i g u r e s 13 and L4.
T h i s i s a bronze c i r c u l a t i n g
pump from an e n g i n e c o o l i n g system. N o r m a l l y t h i s a l l o y
s h o u l d be r e s i s t a n t t o impingement a t t a c k caused by h i g h
f l o w v e l o c i t y or p e r i p h e r a l speeds, p a r t i c u l a r l y i n
a w e l l i n h i b i t e d c o o l i n g water
Yet b o t h the a l l o y and
r o t a t i o n a l speed mus
o f r o t a t i o n was too
o u t e r edge o f the i m p e l l e r r e s e m b l e s impingement a t t a c k .
However, on the r e v e r s e s i d e ( F i g u r e 14) t h e r e i s a
w e l l d e f i n e d zone o f p i t t i n g e x t e n d i n g inward about 2
i n c h e s from the o u t e r r i m . T h i s i n d i c a t e s a,metal i o n
c o n c e n t r a t i o n p r o b l e m . I t has been suggested t h a t i f
we c o u l d c u t t h r o u g h the i m p e l l e r and s e p a r a t e the o u t e r
1/3 from the i n n e r p o r t i o n by an a n n u l a r i n s u l a t i n g
b u s h i n g , i t would be p o s s i b l e t o d e t e c t c u r r e n t f l o w i n g
from one zone t o the o t h e r , when the i m p e l l e r i s t u r n
i n g . C o r r e c t i o n o f t h i s type a t t a c k u s u a l l y r e q u i r e s
e i t h e r a change o f a l l o y t o a more r e s i s t a n t m a t e r i a l ,
or r e d u c t i o n i n r o t a t i o n r a t e . I n t h i s c a s e , a s h a r p l y
i n c r e a s e d c o n c e n t r a t i o n o f chromate c o r r o s i o n i n h i b i t o r
d i d not a r r e s t the a t t a c k .
M a n - f a i l u r e s i n maintenance o f i n h i b i t o r c o n c e n
t r a t i o n s o f t e n c o n t r i b u t e to c o r r o s i o n f a i l u r e s .
Fig
u r e s 15 and 6 i l l u s t r a t e a f a i l e d c a s t i r o n i m p e l l e r
from a s w i t c h e r l o c o m o t i v e c o o l i n g system.
Penetrating
c o r r o s i o n , and c o r r o s i o n p r o d u c t d e p o s i t s i n w e l l - d e
f i n e d p a t t e r n s can be seen on the i n n e r f a c e . On the
o u t e r s i d e behind the vanes a r e deep c o r r o s i o n zones
r e s e m b l i n g c a v i t a t i o n c o r r o s i o n . A chromate c o r r o s i o n
i n h i b i t o r was used i n the c o o l i n g w a t e r . I n v e s t i g a t i o n
d i s c l o s e d t h a t n i g h t l y o v e r f i l l i n g w i t h u n t r e a t e d make
up water was o v e r f l o w i n g the c o o l i n g system, and d i l u t
i n g the i n h i b i t o r t o a n o n - p r o t e c t i v e l e v e l . A f t e r
c o m p l e t i n g r e p a i r s , the system was r e f i l l e d and i n h i b i
tor level, adjusted.
The f i l l i n g c o n n e c t i o n then was
s e a l e d and l o c k e d t o p r e v e n t f u r t h e r u n t r e a t e d water
a d d i t i o n . T h i s e l i m i n a t e d the pump c o r r o s i o n problem.
D e z i n c i f i c a t i o n of Brass.
Two
forms o f
dezincification

CORROSION
372
Figure 11.
Figure 12.
Typical attack location, oxygen concentration cell
Typical attack location, metal-ion concentration cell

CHEMISTRY
WILKES
Figure 13.
Industrial
Problems
373
Bronze impeller of circulating pump damaged by impingement attack

and concentration cells

374
CORROSION CHEMISTRY
Figure 14.
Band of concentration cell corrosion damage on bronze pump impeller

WILKES
Industrial
Figure 15.
Problems
Cast-iron pump impeller with cavitation corrosion damage

376
Figure 16.
Opposite face of cast-iron impeller penetrated by cavitation corrosion.

Note pattern of corrosion products deposition.

11.
WILKES
Industrial
Problems
377
a r e e n c o u n t e r e d i n heat exchanger t u b e s , p i p i n g and

brass headers.
In layer type d e z i n c i f i c a t i o n , attack
proceeds r e l a t i v e l y u n i f o r m l y from the water
side.
A f f e c t e d a r e a s c a n be d i s t i n g u i s h e d by t h e d u l l r e d
c o l o r of the c o p p e r - r i c h areas where z i n c has d i s s o l v e d
away.
Layer d e z i n c i f i c a t i o n usually proceeds u n t i l
l o s s of s t r e n g t h or p e n e t r a t i o n to the root of
threaded
a r e a s a l l o w s the component to f a i l m e c h a n i c a l l y .
It
g e n e r a l l y o c c u r s i n low h a r d n e s s , low pH c o o l i n g
water,
i n the absence of p r o p e r c o r r o s i o n i n h i b i t i o n , and
i s a c c e l e r a t e d by c h l o r i d e s and s u l f a t e s .
A more d a n g e r o u s f o r m o f d e z i n c i f i c a t i o n , known
P l u g t y p e , causes p e n e t r a t i o n f a i l u r e s and s e r i o u s
leaks.
In plug type a t t a c k , zinc i s s e l e c t i v e l y d i s s o l v e d , with copper being l e f t behind.
I n some c a s e s
i t appears t h a t b o t h z i n c and copper d i s s o l v e ,
with
copper being redeposite
the c o r r o s i o n spot.
i d e n t i f i e d by t h e d i s t i n c t i v e r e d s p o t s o f spongy
copper
w h i c h show up on t h e y e l l o w b r a s s s u r f a c e .
It is dangerous because of the speed w i t h which l e a k s can o c c u r .
Layer type d e z i n c i f i c a t i o n u s u a l l y takes longer
to
reach f a i l u r e .
F i g u r e 17 s h o w s z o n e s o f p l u g t y p e
attack i n the w a l l of a brass p i p e .
F i g u r e 18 s h o w s
a f a i l e d A d m i r a l t y b r a s s tube w a l l , both unetched and
etched.
The spongy copper p l u g i s e a s i l y s e e n .
In
the etched specimen the normal g r a i n p a t t e r n of
Alpha
b r a s s and the porous copper p l u g i n the p i t t e d a r e a a r e
shown.
I n c o l o r , t h e undamaged b r a s s i s y e l l o w - g o l d ,
while the d e z i n c i f i e d plug i s d u l l r e d .
Properly maintained chromate concentrations i n c o o l i n g water are
specifically effective
i n prevention of d e z i n c i f i c a t i o n .
But the best long term p r o t e c t i o n involves redesign
to
e l i m i n a t e z i n c , or at l e a s t , to replace h i g h - z i n c b r a s ses (such as 60-40 y e l l o w brass) w i t h l o w - z i n c
copper
alloys;
(80-10-10 or 85-5-5-5 red brass are good).
I n h i b i t e d b r a s s ( c o n t a i n i n g 1/2% a r s e n i c o r 0 . 1 %
antimony) a l s o a r e e x c e l l e n t i n p r e v e n t i o n o f d e z i n c i f i c a tion.
a
Aluminum F a i l u r e s .
Many D i e s e l e n g i n e c o o l i n g
systems
were f i r s t c o n s t r u c t e d w i t h aluminum headers and o t h e r
components d i r e c t l y coupled to c a s t i r o n b l o c k s ,
with
copper connections,
bronze s c r e e n s and o t h e r
dangerous
multi-metal couples.
These dangerous
combinations
proved almost impossible to p r o t e c t , even with high
concentrations of chromate c o r r o s i o n i n h i b i t o r s .
In
t h e s e aluminum-copper and a l u m i n u m - i r o n c o u p l e s ,
failure
by c o m p l e t e p e n e t r a t i o n o f 5/8 i n c h aluminum header
p l a t e s o c c u r r e d i n t h r e e months of
service.

378
Figure 17.
Light colored areas show plug-type dezincification in section of brass

pipe


Figure 18. Thin cross-section of admiralty brass tube wall penetrated by plugtype dezincification. (Upper section) specimen polished, unetched. (Lower section) same specimen polished and etched. Magnification about 170 diameters.
380
F i g u r e 19 i s a n e x a m p l e o f a n a l u m i n u m h e a d e r
p l a t e damaged by c o n t a c t w i t h h i g h a l k a l i n i t y ,
high
pH c o o l i n g w a t e r .
F i g u r e 20 i s a p h o t o m i c r o g r a p h o f
one s e c t i o n of the p l a t e , i l l u s t r a t i n g the c r a c k i n g and
e x f o l i a t i o n which occurred.
Hydrogen released during
corrosion reactions causes i n t e r n a l pressure i n f i s s u r e s , a c c e l e r a t i n g s w e l l i n g and s e p a r a t i o n of
this
rolled plate.
U n d e r m a g n i f i c a t i o n o f 250 d i a m e t e r s ,
the c r a c k i n g and s w e l l i n g are c l e a r l y v i s i b l e .
A few
s m a l l n o d u l e s of copper were found s u g g e s t i n g t h a t p r e s e n c e o f c o p p e r a l s o was i n v o l v e d i n t h i s c o r r o s i o n
failure.
I n C a n a d a , a number o f mine sweepers were b u i l t
using a l l non-magnetic m a t e r i a l s .
The e n t i r e e n g i n e
b l o c k was c o n s t r u c t e d o f a c l a d a l u m i n u m a l l o y .
For
c o r r o s i o n i n h i b i t i o n i n the c l o s e d c o o l i n g system, an
inhibitor containin
applied.
The p h o s p h a t e - b a s e
c o r r o s i o n of the engine b l o c k s , r e s u l t i n g i n p e n e t r a tion failures.
Deep p i t t i n g l e a d i n g t o p e n e t r a t i o n o f
t h e c a s t a l u m i n u m b l o c k i s shown i n F i g u r e 2 1 .
Many o f
the p i t s s e r v e d as s t r e s s r a i s e r s , c a u s i n g c r a c k i n g .
A t the base of the p i t s where r e d u c i n g a c t i o n accompan i e s c o r r o s i o n , c o p p e r d e p o s i t i o n c a n be s e e n .
Copper
comes from c o r r o s i o n of b r o n z e c i r c u l a t i n g pumps, p h o s p h o r - b r o n z e f i t t i n g s and copper a l l o y l i n e s .
These
c o o l i n g s y s t e m s c o u l d have been w e l l p r o t e c t e d by a
c h r o m a t e i n h i b i t o r , o r by a b o r a t e - n i t r i t e - M B T p r o d u c t ,
b u t e x p e r i e n c e d a c c e l e r a t e d a t t a c k when u s i n g t h e i m proper phosphate-silicate
inhibitor.
Fretting Attack.
This is. a type of c o r r o s i v e a c t i o n
i n w h i c h m e t a l t r a n s f e r s from one b e a r i n g s u r f a c e
to
a n o t h e r , when v i b r a t i o n o r o t h e r m e c h a n i c a l f o r c e s
cause s l i g h t r e l a t i v e movement.
I n F i g u r e .22 we a r e
l o o k i n g down i n t o t h e o p e n i n g o f a D i e s e l e n g i n e
cylinder block i n t o which a ribbed c y l i n d e r l i n e r i s seated.
Where the r i b s a r e i n c o n t a c t w i t h the e n g i n e
block,
t r a n s f e r o f m e t a l by f r e t t i n g has o c c u r r e d .
Cooling
water c i r c u l a t e s between the b l o c k and the l i n e r .
To
p r e v e n t c r e v i c e a t t a c k between l i n e r r i b s and e n g i n e
b l o c k , and a v o i d i n i t i a t i o n of f r e t t i n g damage,
both
e n g i n e b l o c k and l i n e r s u r f a c e s s h o u l d have been p r e treated ("pickled")
with a strong concentration of
a l k a l i n e c h r o m a t e i n h i b i t o r (1% t o 5% s t r e n g t h ) , b e f o r e
attempting to seat the l i n e r .
F i g u r e 2_3 s h o w s t h e
ribbed area at top of the l i n e r .
Absence of
adequate
c o r r o s i o n c o n t r o l o f t h i s c o o l i n g s y s t e m i s shown by
s e v e r e c r e v i c e c o r r o s i o n and f r e t t i n g damage on t h e
c o n t a c t f a c e s o f l i n e r r i b s , and a l s o by t h e e x t e n s i v e

CO
oo
header plate failed by exfoliation corrosion and

cracking
Wrought-aluminum
Figure 19.

382
Figure 20.
Section of failed aluminum plate showing cracking and exfoliation

(magnification 215 diameters)

WILKES
Figure 21.
Industrial
Problems
383
Section of clad-aluminum engine block which failed by pitting during

use of improper inhibitor in coolant

384
Figure 22.
Fretting attack inside engine jacket at contact points with ribbed

cylinder liner

11.
WILKES
Figure 23.
Industrial
Problems
385
Cylinder-liner ribs show metal loss by fretting attack and crevice corrosion plus "worm holing" attack on liner at base of ribs

CORROSION
386
'worm h o l e ' c o r r o s i o n i n l i n e r
s t r e s s e d region at the base of
w a l l s , i n the
liner
ribs.
CHEMISTRY
severely
Cavitation-Corrosion.
T h i s form of c o r r o s i o n a t t a c k ,
which causes l o c a l i z e d f a i l u r e s of c y l i n d e r l i n e r s
i n D i e s e l e n g i n e s , has been r e s p o n s i b l e for
serious
m a i n t e n a n c e p r o b l e m s i n power u n i t s of t r u c k s , b u s e s ,
r a i l w a y l o c o m o t i v e s and m a r i n e t r a n s p o r t .
The
concent r a t e d a r e a of a t t a c k , and s e v e r i t y of c o r r o s i o n
are
c l e a r l y shown i n F i g u r e 2.
The a r e a s of
greatest
a t t a c k o c c u r 90 d e g r e e s f r o m t h e c r a n k s h a f t c e n t e r
line
o n t h e t h r u s t o r c o m p r e s s i o n s i d e ; a l i g h t e r a t t a c k may
appear on the o p p o s i t e s i d e .
Other c h a r a c t e r i s t i c s
s h o w n i n F i g u r e 2_5 i n c l u d e : 1) H o n e y c o m b e d
appearance
of corroded metal.
2) C o r r o d e d s u r f a c e s s u b s t a n t i a l l y
free of c o r r o s i o n products.
3) A t t a c k o c c u r s i n s h a r p l y
defined areas, irregula
boundaries between a f f e c t e
C a v i t a t i o n c o r r o s i o n of c y l i n d e r l i n e r s i s not
c a u s e d by h i g h v e l o c i t y w a t e r f l o w , nor by i m p i n g e m e n t
of coolant streams.
Rather, i t appears that v i b r a t o r y
effects are p r i m a r i l y responsible.
Under the tremendous s t r e s s e s of f u e l c o m p r e s s i o n and c o m b u s t i o n i n the
D i e s e l c y c l e , t h e s e 3/4 i n c h t h i c k c y l i n d e r l i n e r s
v i b r a t e o r " r i n g " a t f r e q u e n c i e s e s t i m a t e d t o be i n
the range of 7,000 to 8,000 c y c l e s per second,
and
higher.
In v i b r a t i n g at such high frequencies,
the
liner
m e t a l i s " j e r k e d " away f r o m c o o l i n g w a t e r c o n t a c t i n g
the s u r f a c e so r a p i d l y as to reduce l o c a l c o o l a n t
pressure below the vapor pressure of the coolant
fluid,
forming minute v a p o r - f i l l e d c a v i t i e s , or
"bubbles."
When t h e r e v e r s e v i b r a t i o n c y c l e o c c u r s , t h e v a p o r f i l l e d c a v i t i e s i n s t a n t l y implode or c o l l a p s e .
The r e c u r r i n g c o l l a p s e and r e f o r m a t i o n of v a p o r - f i l l e d c a v i ties occurs i n microseconds.
Because the
"bubbles"
form and c o l l a p s e so r a p i d l y , the energy they r e l e a s e
is
measured i n hundreds of tons per square i n c h .
From
study of photomicrographs of f a i l e d m e t a l , i t a l s o
a p p e a r s t h a t when t h e s e v a p o r c a v i t i e s i m p l o d e o r
coll a p s e , they d r i v e water and water vapor r i g h t i n t o
the g r a i n s t r u c t u r e .
When t h e v a p o r c a v i t i e s f o r m
a g a i n , and p r e s s u r e i s r e l i e v e d t r a p p e d water vapor
explodes upward.
P h o t o m i c r o g r a p h s show t h a t c r y s t a l l i n e s t r u c t u r e h a s been d i s t o r t e d and r e a r r a n g e d by t h e
tension e f f e c t s of escaping water vapor.
The unwanted e n g i n e v i b r a t i o n i s r e l a t e d to c r a n k s h a f t r o t a t i o n a l s p e e d , b u t i s c a u s e d by e n g i n e i m b a l a n c e , c r a n k s h a f t m i s a l i g n m e n t , or e x c e s s i v e wear of
^ " l i n d e r l i n e r s and p i s t o n s on the t h r u s t s i d e .
In

WILKES
Industrial
Problems
Corrosion
Figure 24.
Vibratory cavitation corrosion of large diesel engine cylinder which

progressed to perforation (7)

388
Figure 25. Concentrated zone of loss, absence of corrosion products, and sharply
defined boundaries identify cavitation-corrosion attack on cylinder liner

11.
WILKES
Industrial
Problems
389
discussing mechanical/physical f a c t o r s c o n t r i b u t i n g to
c a v i t a t i o n - c o r r o s i o n o f c y l i n d e r l i n e r s , S p e l l e r and
LaQue (J) made the f o l l o w i n g s u g g e s t i o n s :
1)
Reduce l i n e r v i b r a t i o n by any p r a c t i c a b l e means;
i . e . , r e d e s i g n i n g l i n e r s u p p o r t s t o i n t r o d u c e dampening
e f f e c t s , or p r o v i d i n g
cushioning.
2)
Develop and use h a r d e r , more r e s i s t a n t l i n e r m e t a l s .
(Hard a l l o y c a s t i r o n l i n e r s respond b e t t e r t o c o r r o s i o n i n h i b i t i o n than do s o f t c a s t i r o n l i n e r s . )
3)
Reduce o p p o r t u n i t y f o r development o f vapor c a v i t i e s by o p e r a t i n g a t h i g h e r p r e s s u r e s and t e m p e r a t u r e s
i n c o o l i n g s y s t e m s , and p o s s i b l y by i n t r o d u c t i o n o f a i r
b u b b l e s as c u s h i o n s a g a i n s t v a p o r - c a v i t y c o l l a p s e .
4) M a i n t a i n chromate c o r r o s i o n i n h i b i t o r s i n c o o l i n g
water a t c o n c e n t r a t i o n s above 2,000 mg/1
(as C r O ^ ) ,
and h o l d c o o l a n t pH w i t h i n the range o f 8.5-9.5.
5)
Include s u i t a b l
between c o r r o s i o n i n h i b i t o r
F i e l d e x p e r i e n c e showed t h a t c y l i n d e r l i n e r s c o u l d
not be p r o t e c t e d a g a i n s t c a v i t a t i o n - c o r r o s i o n by p l a t i n g
w i t h chromium or h a r d e r m e t a l s , or by p l a s t i c c o a t i n g s .
Both would e x p l o d e o f f a t the same r a t e as d i d the
o r i g i n a l l i n e r m e t a l . But t e s t s showed t h a t s i n c e
c o r r o s i o n f a c t o r s were i n v o l v e d , as w e l l as m e c h a n i c a l /
p h y s i c a l f a c t o r s , new c y l i n d e r l i n e r s c o u l d be p r o t e c t e d
a g a i n s t c a v i t a t i o n c o r r o s i o n by p r o p e r
concentrations
o f a l k a l i n e chromate i n h i b i t o r s . C a v i t a t i o n a t t a c k i n
p r o g r e s s might not be a r r e s t e d on o l d e r l i n e r s o f eng i n e s w i t h s e v e r e v i b r a t i o n a l p r o b l e m s , even when u s i n g
chromtes. But on newer e n g i n e s , p r o p e r l y i n h i b i t e d
w i t h chromate from the f i r s t day o f s e r v i c e , c a v i t a t i o n
c o r r o s i o n c o u l d be c o m p l e t e l y p r e v e n t e d .
One o t h e r i n h i b i t o r type t h a t w i l l p r e v e n t c a v i t a t i o n - c o r r o s i o n i s the s o l u b l e o i l t y p e , which i n c o r p o r a t e s a l i g h t m i n e r a l o i l p l u s e m u l s i f i e r s and a d s o r p t i o n - t y p e i n h i b i t o r s , such as o r g a n i c amines. U n f o r t u nately, although e f f e c t i v e i n c o n t r o l l i n g c a v i t a t i o n ,
( p o s s i b l y by c u s h i o n i n g e f f e c t s o f the adsorbed o i l
r e i n f o r c e d f i l m ) they s o f t e n and damage rubber connect o r s and s e a l s , cause l e a k a g e and water l o s s . When
e m u l s i f i e r s are e x h a u s t e d , the o i l e m u l s i o n b r e a k s , and
a l l o w s o i l y f i l m s t o form on heat t r a n s f e r s u r f a c e s .
Some of the amine type e m u l s i f i e r s and i n h i b i t o r s are
p o t e n t i a l l y d e s t r u c t i v e t o copper a l l o y s i n the c i r c u l a t i n g system, a l s o . One o t h e r type i n h i b i t o r t h a t has
been used e f f e c t i v e l y f o r many y e a r s i n c l o s e d c o o l i n g
systems i s g e n e r i c a l l y i d e n t i f i e d as " b o r a t e - n i t r a t e . "
These c o m b i n a t i o n s use sodium n i t r i t e , b u f f e r e d by
a l k a l i n e b o r a t e s , and s i l i c a t e s w i t h s u p p l e m e n t a l i n h i b i t o r s such as m e r c a p t o b e n z o t h i a z o l e , t h i a z o l e or benzo-

390
CORROSION CHEMISTRY
triazole to protect copper alloys in the system. The

working concentration is about twice as high as that re
quired for chromate inhibitors. Borate-nitrites are
not always effective in suppression of cavitation-corro
sion in affected systems, but otherwise have given
excellent protection of closed cooling systems.
For control of deposits and scale, closed systems
require hardness-free (or preferably mineral-free)
makeup water. Microbicides are not required for closed
systems, but dispersants to keep metal oxides and other
insoluble contaminants in suspension are useful. They
aid in preserving clean heat transfer surfaces, which
provide maximum response to corrosion inhibition. Long
chain ethylene oxide polymers also are being used to
improve "wetting" properties of cooling water and mini
mize turbulence, where impingement and cavitation prob
lems are observed.
Literature Cited
1.
2.
3.
4.
5.
6.
7.
Langelier, W. F., Journal American Water Works

Association, (1936), 28, (No. 10), 1500-1521.
Langelier, W. F., Journal American Water Works
Association, (1946), 38, (No. 2), 169-178 and
179-185.
Crum, Ferris B., and Wilkes, John F., U.S. Patent
No. 2 783 200, (February 26, 1957).
Denman, Wayne L. and Hwa, Chih ., Canadian Patent
No. 580 658, (August 4, 1959). Reissued as Cana
dian Patent No. 717 433, (March 28, 1961).
Zimmie, William E. and Bloecher, Frederick W., Jr.,
U.S. Patent No. 3 080 264, (March 5, 1963).
Zimmie, William E. and Bloecher, Frederick W., Jr.,
U.S. Patent No. 3 085 916, (April 16, 1963).
Speller, Frank N. and LaQue, Francis L., Corrosion,
(1950), 6, (No. 7), 209-215.
RECEIVED
September 1, 1978.

12
High-Temperature Corrosion in Coal Gasification Plants
V. L. HILL, D. YATES, and B. A. HUMPHREYS
IIT Research Institute, 10 West 35 Street, Chicago, IL 60616
Coal represents the greatest domestic r e s e r v o i r of

fossil
energy a v a i l a b l e at the present time. Thus, i t
is l i k e l y i n the nea
supply increasingl
consumed energy. While greater usage of coal for direct combustion is being projected, g a s i f i c a t i o n of
coal is an a l t e r n a t i v e to dwindling natural gas supplies.
Gas produced by g a s i f i c a t i o n can vary from low
to high heating value depending on the g a s i f i c a t i o n
process employed. Low- and medium-Btu gas could be
used for e l e c t r i c power generation, space heating, and
i n d u s t r i a l a p p l i c a t i o n s . High-Btu gas produced by gasification
can be used as a replacement for n a t u r a l gas.
G a s i f i c a t i o n of coal producing low- to medium-Btu
gas is not a new process.
However, several new gasifi c a t i o n processes designed for greater conversion
efficiency are under development.
The second and t h i r d
generation processes generally operate at higher temperatures and pressures than current g a s i f i c a t i o n
plants.
In a d d i t i o n , the current non-domestic processes are based on use of low-sulfur European coals.
Accordingly, the construction materials currently employed i n these plants may not be suitable for conversion of h i g h - s u l f u r eastern coals.
The combination of
higher plant operating temperatures and pressures and
high sulfur concentration may reduce the a v a i l a b l e materials
for plant construction.
Materials problems i n newer coal g a s i f i c a t i o n processes accrue generally from operating temperatures of
1 5 0 0 - 2 8 0 0 F and pressures of 150-1200 psi. Added to
these conditions are low oxygen a c t i v i t y and high s u l fur a c t i v i t y i n the product gas atmosphere.
Finally,
coal ash and sulfur sorbents present i n the system can
cause materials f a i l u r e by corrosion and/or erosion- c o r r o s i o n . Current m e t a l l i c alloys that were developed
0-8412-0471-3/79/47-089-391$05.75/0

392
CORROSION
CHEMISTRY
f o r h i g h oxygen and l o w s u l f u r a c t i v i t y e n v i r o n m e n t s
are subject t o o x i d a t i o n - c o r r o s i o n or e r o s i o n - c o r r o s i o n
i n t h e g a s i f i e r environment.
Background
P r i o r t o 1972, no i n f o r m a t i o n e x i s t e d on t h e behavior o f high-temperature m a t e r i a l s i n g a s i f i c a t i o n
e n v i r o n m e n t s . M a t e r i a l s d a t a were a v a i l a b l e f o r h i g h p r e s s u r e equipment a t low o p e r a t i n g t e m p e r a t u r e s , o r
f o r l o w - p r e s s u r e equipment a t h i g h o p e r a t i n g temperat u r e s . The emerging c o a l g a s i f i c a t i o n p r o c e s s e s ,
t h e r e f o r e , r e p r e s e n t e d a new environment f o r h i g h temperature m a t e r i a l s . Behavior o f m a t e r i a l s , both
m e t a l l i c and r e f r a c t o r y , c o u l d n o t be p r e d i c t e d b a s e d
on t h e i r performance on t h e n - e x i s t i n g equipment.
D u r i n g 1972 t h
p o r t e d by t h e America
f o r t s i n coal g a s i f i c a t i o n materials research. Since
1975 t h e m a j o r s u p p o r t f o r t h e program has been supp l i e d by t h e Department o f Energy i n c o o p e r a t i o n w i t h
AGA. F i v e phases o f e f f o r t have been d e f i n e d , w i t h work
i n p r o g r e s s . These a r e a s a r e : Phase I - L a b o r a t o r y
H i g h Temperature O x i d a t i o n - C o r r o s i o n ; Phase I I - P i l o t
P l a n t C o r r o s i o n S t u d i e s ; Phase I I I - Quench System
Aqueous C o r r o s i o n ; Phase I V - H i g h Temperature E r o s i o n C o r r o s i o n ; and Phase V - M e c h a n i c a l P r o p e r t y Measurements, The f i r s t f o u r phases a r e b e i n g c o n d u c t e d a t
the I I T Research I n s t i t u t e .
A major p o t e n t i a l problem f o r c o a l g a s i f i c a t i o n
m a t e r i a l s due t o h i g h - s u l f u r c o a l s i s i n d i c a t e d by
T a b l e I , The t a b l e compares t h e m e l t i n g p o i n t s o f s u l f i d e s and e u t e c t i c t e m p e r a t u r e s o f t h e m e t a l - m e t a l
s u l f i d e systems f o r i r o n , n i c k e l , c o b a l t , and c h r o m i um ( 1 ) . I t may be seen t h a t t h e m e t a l - m e t a l s u l f i d e
e u t e c t i c t e m p e r a t u r e s v a r y from 1193F f o r n i c k e l t o
2462F f o r chromium. A l l t h r e e e l e m e n t a l bases o f
h i g h - t e m p e r a t u r e a l l o y s , i r o n , n i c k e l , and c o b a l t , exh i b i t e u t e c t i c t e m p e r a t u r e s o f 1810F o r l e s s . The
n i c k e l - n i c k e l s u l f i d e e u t e c t i c i s 1193F.
The s i g n i f i c a n c e o f t h e e u t e c t i c t e m p e r a t u r e s
shown i n T a b l e I i s t h a t i n h i g h - s u l f u r gases m e l t i n g
of c o r r o s i o n products o f high-temperature a l l o y s can
occur w i t h i n t h e i r normal o p e r a t i n g range. Molten corr o s i o n products a r e not developed d u r i n g a i r o x i d a t i o n .
F u r t h e r m o r e , n i c k e l - c h r o m i u m a l l o y s a r e g e n e r a l l y emp l o y e d i n a i r e n v i r o n m e n t s a t h i g h e r o p e r a t i n g tempera t u r e s because o f t h e i r h i g h e r s t r e n g t h and o x i d a t i o n
resistance.
I n s u l f u r - c o n t a i n i n g atmospheres t h e s e
a l l o y s a r e most s u s c e p t i b l e t o m e l t i n g .
Iron-base

12.
HILL ET AL.
Coal-Gasiftcation
Plants
393
a l l o y s w o u l d be e x p e c t e d t o have t h e h i g h e s t m e l t i n g
t e m p e r a t u r e s , but a r e g e n e r a l l y l e s s o x i d a t i o n r e s i s t a n t and/or have l o w e r s t r e n g t h .
Thus, a l l o y s e l e c t i o n
f o r h i g h - t e m p e r a t u r e c o a l g a s i f i c a t i o n s e r v i c e tends t o
be t h e i n v e r s e o f t h a t a p p l i c a b l e t o h i g h - t e m p e r a t u r e
air oxidation.
O x i d a t i o n - c o r r o s i o n data i n c l u d e d i n t h i s paper
were g e n e r a t e d i n Phases I and I I o f the program.
Other phases o f the I1TRI work have been d e s c r i b e d i n
current l i t e r a t u r e (2-9).
M e t a l l o s s i n t E i s program has g e n e r a l l y r e s u l t e d
f r o m t h e combined e f f e c t s o f oxygen and s u l f u r .
Thus,
the term o x i d a t i o n - c o r r o s i o n i s u s e d i n t h i s paper t o
d e f i n e m e t a l l o s s , No a t t e m p t i s made t o s e p a r a t e the
i n d i v i d u a l e f f e c t s o f t h e c o r r o d e n t s p e c i e s s i n c e chemi c a l a n a l y s i s o f the c o r r o s i o n p r o d u c t s was n o t conducted.
Results
Phase 1 - L a b o r a t o r y High-Temperature C o r r o s i o n
Testing.
The Phase I c o r r o s i o n program began i n 1973
w i t h d e s i g n and f a b r i c a t i o n o f two r e a c t o r s c a p a b l e o f
o p e r a t i n g t o 2000F a t 1000 p s i . T e s t i n g i n a t y p i c a l
c o a l g a s i f i c a t i o n atmosphere began i n 1973.
To d a t e ,
o v e r 40,000 h r s of t e s t i n g have been completed i n the 2
r e a c t o r s i n v o l v i n g 57 c o m m e r c i a l and d e v e l o p m e n t a l
a l l o y s and c o a t i n g s .
D e t a i l s o f the t e s t equipment
have been r e p o r t e d e l s e w h e r e (2) and w i l l , t h e r e f o r e ,
n o t be d i s c u s s e d i n t h i s p a p e r .
The g a s i f i e r atmosphere u s e d f o r most Phase I c o r r o s i o n t e s t s i s given i n Table I I . During t e s t i n g ,
o n l y the i n l e t gas c o m p o s i t i o n shown was c o n t r o l l e d .
The t e m p e r a t u r e - p r e s s u r e dependent e q u i l i b r i u m gas comp o s i t i o n s shown r e p r e s e n t the a c t u a l t e s t gas composit i o n a t each t e s t temperature.
G e n e r a l l y , the e q u i l i b r i u m gas c o m p o s i t i o n was o b t a i n e d i n the r e a c t o r by
i n t e r a c t i o n o f the i n l e t gas s p e c i e s .
T h i s was v e r i f i e d by a n a l y s e s o f t h e r e a c t o r e x i t gas i n a gas
chromato graph.
The c o m p o s i t i o n s o f the a l l o y s e v a l u a t e d i n Phase
I are summarized i n T a b l e I I I . These a l l o y s r e p r e s e n t
most c l a s s e s o f h i g h - t e m p e r a t u r e i r o n - , n i c k e l - , and
c o b a l t - b a s e a l l o y s t h a t c o u l d be c o n s i d e r e d f o r c o a l
g a s i f i c a t i o n s e r v i c e . Pack a l u m i n i z e d and c h r o m i z e d
c o a t i n g s on A I S I 310 and IN-800 were a l s o e v a l u a t e d i n
the t e s t program.
C o r r o s i o n data contained i n t h i s paper are not i n t e n d e d t o summarize the r e s u l t s f o r the 57 a l l o y s and
c o a t i n g s exposed f o r p e r i o d s o f up t o 5000 h r .
Rather,

394
CORROSION
CHEMISTRY
Table I
EUTECTIC TEMPERATURES OF SELECTED
METAL-METAL SULFIDE SYSTEMS
3
MP o f
Sulfide
Eutectic
Ni-Ni S2
3
C0-C04S3
810
932
Sulfur
Concentration
at E u t e c t i c
w/o
a/o
Eutectic
Temperature
""C
1490
645
1193
33.4
21.5
1710
877
1611
40
26.6
Fe-FeS
1190
2174
988
1810
44
31
Cr-CrS
1565
2849
1350
2462
43.9
32.5
Reference 1
b Formed p e r i t e c t i c a l l y .
a
Table I I
INLET AND EQUILIBRIUM GAS COMPOSITION
OF PHASE I CORROSION TESTS
Gas C o m p o s i t i o n , v/o
Gasifier
Component
H
CO
co
CH
NH
Equilibrium
1500F
23
24
900 F
4
18
11
17
12
25
19
15
19
9
1
Inlet
1800F
31
H2S
0-1.0
0-1.0
0-1.0
0-1.0
H 0
Bal
Bal
Bal
Bal
I n l e t gas c o m p o s i t i o n c o n s t a n t f o r a l l t e s t s i n
g a s i f i e r gas.
A t 1000 p s i and i n d i c a t e d
temperature.

12.
HILL
Coal-Gasification
E T A L .
395
Plants
Table III
CHEMICAL COMPOSITION OF ALLOYS SELECTED
FOR TESTING IN PHASE I
C o m p o s i t i o n , w/o
Co
Cr
~NT
Alloy
Series
"AT"
202
0. 05
0. 64
0. 55
71 .02
9. 24
18. 18
304
0. 05
1. 45
0. 54
70. 04
9. 10
18. 76
?16
0. 05
1. 65
0. 43
65. 23
13. ?8
17. 14
309
0. 11
0. 54
0. 74
60. 46
14 70
22. 97
314
0. 06
1. 90
2. 21
51. 64
20. 00
24. 00
310
0. 06
1. 71
0. 68
52. 16
20. 20
25. 00
446
0. 10
0. 45
IN-600
0. 05
0. 15
IN-601
0. 04
0. 24
IN-800
0..03
0. 80
0..33
47. ,08
30. 84
20. 60
0.,10
32
0,.03
0.,72
0..40
43..22
32..22
21..40
0,.02
.76
0..03
0..03
0..03
0..30
48, 40
50..00
0,.01
HC 250
3,.03
0..5
0,.7
68,.1
0,.1
27,.5
0.1
HD 45
0,.48
0,.7
1 .5
62,.1
5,.2
29,.9
0.1
HL 40
0 .47
0,.6
1 .4
47 .1
19,.4
30 .9
0.1
HL
0 .42
0 .7
2 ,4
45 .8
19 3
31 .4
RA-333
0 .05
1 .5
1 .4
15 .5
47 .5
26 .2
C r u t e m p 25
0 .07
1 .5
0 .6
47 .2
24 .8
25 .4
M u l t i m e t N155
0 .11
1 .4
0 .7
29 .1
19 .8
21 .8
19 .5
H a y n e s 150
0 .06
0. S
0 .2
16 .5
1 .7
27 .9
49 .6
H a y n e s 188
0 .08
0 .7
0 .4
1 .4
23 .3
23 .4
35 .7
S t e l l i t e 6B
1 .0
1 .4
0 .6
2 .0
2 .4
28 .5
56 .4
VE 441
0 .03
0 .1
0 .1
SI .5
0 .004
0 .2
2 .3
0 .04
8 .2
0 .7
62 .9
312
0.15
0.5
Bal
30
329
0.05
0.4
Bal
4.,3
27.1
29
310(A1)
310(Cr)
0.42Ti
IN-800(A1)
IN-SOO(Cr)
IN-793
IN-671
(50/50)
Ser i e s
40-3Si
Nl
Armco
21-6-9
0 .20
0 .01
0.1
0.4
0 .01
90 .0
2 .8
6 .8
20 .7
2.7W
3.8
3 .0
1.1 Cb+Ta,
3.9W
3.0
0.1
0 .22
0.6
.051 La, 14.6 W
1.1
6.5W
15 .1
3.2
0.04Zr
4 .4
0.1
0.22
S e r i e s 3a
AL
29-4-4
0.005
Bal
4.,0
AL
EX-20
1.0
Bal
20
1.4
5
30
12W
Bal
Co-Cr-W No. 1
2.5
Thermalloy
0.4
Bal
35
26
0.55
Bal
47
27
12.5
22.0
18.5
Bal
21.8
2.5
Bal
21.5
0.2
31
21
0.35
41
21.5
0.10
Wiscalloy
63WC
30/50N
A r m c o 18SR
0.05
Armco
0.06
22-13-5
1.0
0.15
1.0
1.0
I n c o n e l 625
0.05
0.25
0.25
S a n i c r o 32X
0.08
I n c o l o y 825
0.03
Hastelloy
Bal
0.50
0.25
30
4W
0.40Ti
18.0
Bal
Bal
5.0
5W
15
2.5
2.0
0.20Cb,
0.20V, 0.3N
9.0
0.6W
9.0
0.2Ti,3.65Cb
0.35Ti,
3.0

3W
2.25Cu,0.9Ti
396
CORROSION
CHEMISTRY
Tabl
_C
Alloy
si
> w/ V
Fe
Co
Series
0.25
1.,0
1.,0
2.0
10.5
29.5
HK
40
0.4
2.,0
2..0
Bal
20
28
HK
40-3S
0.35/
0.45
2.,0
3.,0
Bal
18/22
24/28
Thermalloy
63
0.4
Bal
35
26
Thermalloy
63W
0.40
Bal
35
26
35.0
19.0
50
48
0.05
1..5
1,.25
43
IN-657
IN-738
0.17
0..2
0..3
0.5
556
0.1
1..5
0..4
Bal
20
54
0..2
0,.2
Bal
Bal
Ho
Other
3b
FSX-414
RA-330
Al "
16.0
Bal
8.5
3.4
7.0W
0.5
0.5
1.75
5W
1.5Cb
2.6W,0.9Cb
617
0.07
AL-16-5-Y
0.006
22
20
22
12.5
15.8
0.3
3.0
1.0
5.4

2.5W,0.02La,
1.0Cb+Ta
0.41Y
12.
HILL ET AL.
Cocil-Gasification
Plants
397
r e s u l t s are presented to i n d i c a t e s i g n i f i c a n t trends i n

o x i d a t i o n - c o r r o s i o n d a t a p r o d u c e d by v a r i a t i o n o f h i g h
t e m p e r a t u r e and H2S c o n c e n t r a t i o n s f o r s e l e c t e d a l l o y s .
C o r r o s i o n i n Phase I was a s s e s s e d by m e t a l l o g r a p h i c
measurements o f m e t a l l o s s due t o b o t h s c a l i n g and i n ternal corrosion.
G r a v i m e t r i c a n a l y s i s was employed
o n l y to augment s c a l i n g l o s s measurements. S c a l i n g and
i n t e r n a l c o r r o s i o n were combined t o o b t a i n a c o r r o s i o n
p a r a m e t e r d e f i n e d as t o t a l c o r r o s i o n , o r sound m e t a l
l o s s . T o t a l c o r r o s i o n was t h e n e x t r a p o l a t e d t o m e t a l
l o s s r a t e s i n m i l s / y r (mpy) o n l y as a means o f compari n g the a l l o y s exposed f o r v a r i o u s t i m e s .
As w i l l be
seen s u b s e q u e n t l y , l i n e a r e x t r a p o l a t i o n , i n t e n d e d t o be
conservative, r e s u l t e d i n serious underestimation
of
y e a r l y m e t a l l o s s r a t e s f o r some a l l o y s .
Often k i n e t i c a l l y c o n t r o l l e d t r a n s i t i o n s to h i g h e r c o r r o s i o n r a t e s ,
usually with melting
o f 1000-5000 h r at 1800F
B o t h the H2S c o n c e n t r a t i o n o v e r the range o f
0-1.0
v/o o f the CGA gas and the t e m p e r a t u r e c o n t r o l l e d t h e
measured c o r r o s i o n r a t e s . F i g u r e 1 i l l u s t r a t e s the
e f f e c t o f t e m p e r a t u r e on c o r r o s i o n r a t e s o f s e v e r a l
a l l o y s and c o a t i n g s i n t h e CGA gas c o n t a i n i n g 1 v/o
H2S.
A l l o y s A I S I 309, A I S I 310, and IN-800 d e m o n s t r a t e
a c l e a r t e m p e r a t u r e dependence o f t o t a l o x i d a t i o n c o r r o s i o n i n 1000 h r . The 309 a l l o y had a s c a t t e r band
o f 5 t o 125 m i l s t o t a l m e t a l l o s s f o r f o u r specimens a t
1650F. T h i s i s t y p i c a l o f b o r d e r l i n e a l l o y s t h a t
undergo time-dependent t r a n s i t i o n s t o a c c e l e r a t e d c o r r o s i o n r a t e s . T o t a l c o r r o s i o n o f a l u m i n i z e d 310 and
800 was r e l a t i v e l y u n a f f e c t e d by t e m p e r a t u r e o v e r the
range o f 1500-1800F f o r 1000 h r e x p o s u r e s .
The e f f e c t o f H2S c o n c e n t r a t i o n on t o t a l c o r r o s i o n
o f s e l e c t e d a l l o y s i n 1000 h r a t 1800F i s i l l u s t r a t e d
i n F i g . 2.
A v a r i e t y of d i f f e r e n t o x i d a t i o n - c o r r o s i o n
b e h a v i o r s were o b s e r v e d . F e r r i t i c a l l o y s , l i k e A I S I 446,
g e n e r a l l y showed i n c r e a s e d c o r r o s i o n r a t e w i t h d e c r e a s i n g H2S c o n c e n t r a t i o n , whereas 300 s e r i e s a u s t e n i t i c s
t y p i f i e d by A I S I 310 g e n e r a l l y e x h i b i t e d maxima a t b o t h
0.1 and 1.0 v/o H2S.
IN-800 had h i g h c o r r o s i o n o n l y
above 0.5 v/o H2S.
A l u m i n i z e d A I S I 310 and IN-800, IN671, and s e v e r a l high-chromium a l l o y s d i d n o t i n d i c a t e
a s t r o n g dependence o f H2S c o n c e n t r a t i o n i n 1000 h r
t o t a l corrosion.
Cobalt-base a l l o y s also g e n e r a l l y
p e r f o r m e d as shown f o r the a l u m i n i z e d A I S I 310 and IN671 specimen.
Weight change o f c o r r o s i o n - r e s i s t a n t S e r i e s 1
a l l o y s d u r i n g a 5000 h r e x p o s u r e a t 1800F i n the CGA
atmosphere c o n t a i n i n g 0.5 v/o H2S i s shown i n F i g . 3.
The A I S I 446 and 314 s t a i n l e s s s t e e l s i n d i c a t e d

CORROSION CHEMISTRY
398
60
50
125
Legend
IN-800
IN-800(A1)
A I S I 310
125
310(A1)
AISI
A I S I 309
40
30
20
10
1500
1800
1650
Temperature, F
Figure 1.
Effect of temperature on 1000-hour total corrosion of selected alloys in

CGA environment containing 1 v/o H S
2

12.
HILL ET AL.
Coal-Gasification
Plants

399
400
+20
-20
-40
Legend
-60
-80
AISI 309
AISI 314
AISI 446
IN-800(A1)
IN-800
IN-671
1000
2000
3000
4000
J L
5000
Time, hr
Figure 3.
Weight change of selected alloys during 5000-hour exposure at 1800F

in CGA atmosphere containing 0.5 v/o H S
2

12.
HILL ET AL.
Coal-Gasification
Plants
401
t r a n s i t i o n s to higher o x i d a t i o n - c o r r o s i o n (weight l o s s )
a f t e r 1000 h r . A l t h o u g h not shown, s i m i l a r b e h a v i o r
was o b s e r v e d f o r A I S I 310 s t a i n l e s s s t e e l .
A I S I 309
d e m o n s t r a t e d a t r a n s i t i o n t o w e i g h t g a i n a f t e r 4000 h r .
R a p i d t r a n s i t i o n i n the w e i g h t change c u r v e s g e n e r a l l y
was c o i n c i d e n t w i t h the development o f l o c a l i z e d and/or
general m e l t i n g of the c o r r o s i o n products.
These r e s u l t s s u g g e s t the e r r o r s t h a t c o u l d o c c u r i f 1000 h r
d a t a were e x t r a p o l a t e d t o y e a r l y o x i d a t i o n - c o r r o s i o n
r a t e s . To d a t e , t e s t i n g f o r 5000 h r has been c o m p l e t e d
o n l y a t 1800F i n t h e CGA atmosphere c o n t a i n i n g 0.5 v/o
H2S.
The c u r r e n t r e s u l t s o f 5000 h r t e s t s a t 1800F i n
t h e CGA gas c o n t a i n i n g 0.5 v/o H2S are summarized i n
T a b l e IV. Here t h e 1000, 3000, and 5000 h r t o t a l c o r r o s i o n d a t a have been l i n e a r l y e x t r a p o l a t e d t o mpy c o r rosion rates. Severa
A I S I 310, and A I S I 3 1 4 - - t h a
r a t e s o f 20-40 mpy a f t e r 1000 h r i n d i c a t e d t r a n s i t i o n s
t o h i g h e r r a t e s i n 1000-2000 h r . As a r e s u l t , the l i n e a r l y e x t r a p o l a t e d r a t e s a t 3000 h r were g r e a t e r t h a n
80 mpy.
Other a l l o y s , such as HK-40 and IN-617, exh i b i t e d i n t e r n a l p e n e t r a t i o n a t 1000 h r t h a t d i d not
i n c r e a s e s i g n i f i c a n t l y f o r the longer exposures.
For
t h e s e a l l o y s , c o r r o s i o n d a t a o b t a i n e d by l i n e a r e x t r a p o l a t i o n o f 1000 h r d a t a was m a i n t a i n e d f o r 3000 and
5000 h r , r e s p e c t i v e l y . The d a t a shown i n T a b l e IV i l l u s t r a t e t h a t 1000 h r c o r r o s i o n d a t a c o u l d not be l i n e a r l y e x t r a p o l a t e d t o mpy c o r r o s i o n r a t e s f o r a l l
alloys.
I t was n e c e s s a r y to c o n d u c t 5000 h r t e s t s t o
v e r i f y t h e e x i s t e n c e o f i n c u b a t i o n t i m e s o f 1000-4000
h r f o r t r a n s i t i o n s to r a p i d c o r r o s i o n .
M i c r o s t r u c t u r e s o f two a l l o y s exposed i n the CGA
atmosphere a r e p r e s e n t e d i n F i g s . 4 and 5.
The m i c r o s t r u c t u r e o f A I S I 314 exposed 1000 h r a t 1800F i n the
CGA gas c o n t a i n i n g 0 v/o H2S i s shown i n F i g . 4.
The
a d h e r e n t , l a y e r e d s c a l e on t h i s a l l o y c o n s i s t e d o f f o u r t e e n i n d i v i d u a l m e t a l - o x i d e l a y e r s . M e t a l phase v i s i b l e
i n t h e s c a l e was n i c k e l - r i c h c o n t a i n i n g some i r o n , but
was f r e e o f chromium. O x i d e phase was c h r o m i u m - r i c h
t e n d i n g towards a c h r o m i u m - i r o n s p i n e l a t t h e o x i d e m e t a l i n t e r f a c e . T h i s u n u s u a l m i c r o s t r u c t u r e was a l s o
o b s e r v e d on A I S I 309 and 310 exposed under t h e same
c o n d i t i o n s , a l t h o u g h fewer l a y e r s were p r e s e n t .
I n c o n t r a s t , t h e m i c r o s t r u c t u r e o f IN-671 exposed
5000 h r i n the CGA a t 1800F i s shown i n F i g . 5.
Here,
a t h i n , dense t w o - l a y e r e d s c a l e was o b s e r v e d w i t h m i n o r
g r a i n boundary i n t e r n a l c o r r o s i o n . T o t a l m e t a l l o s s i n
5000 h r was about 2 m i l s . The IN-671 ( 5 0 N i - 5 0 C r ) a l l o y
a l o n g w i t h a l u m i n i z e d A I S I 310 and IN-800 g e n e r a l l y

402
T a b l e IV
LINEARLY EXTRAPOLATED CORROSION RATES OF PHASE I ALLOYS
EXPOSED 1000-5000 HR AT 1800F IN CGA ENVIRONMENT
(0.5 v/o H S )
2
<20 mpy
20-40 mpy
40-80 .mpy
IN-671, 3 1 0 ( A 1 ) ,
8 0 0 ( A 1 ) , 188, 6B,
T63WC, FSX-414,
A l l o y X, Co-Cr-WNo. 1, N155, 150,
HL40, RA-333,
Crutemp 25
309, 310,
446, HK40,
IN-800,
1N-617
IN-738,
556, 314
>80 mpy
3000 h r
3 1 0 ( A 1 ) , HL40,
IN-617, 1N-657,
FSX-414, Co-Cr-W
No. 1, 1 5 0
IN-738
32X, 446
3 1 4 * 309,
310, 556*
5000 h r
IN-800, IN-671
8 0 0 ( A l ) , N155,
A l l o y X, 188, 6B
a
HK40,
Crutemp
25, T63WC
RA-333
2000 hr.

12.
HILL E T A L .
Figure 4.
Coal-Gasification
Plants
Surface microstructure of AISI 314 after 1000-hour exposure at 1800F

in CGA gas containing 0 v/o H S. eg. No. 42225 (170X ).
2
Figure 5.
Surface microstructure of IN-671 after 5000-hour exposure at 1800 F

in CGA gas containing 0.5 v/o H S. eg. No. 44911 (170X)
2

403
404
provided excellent oxidation-corrosion resistance i n

the CGA atmosphere a t a l l H2S c o n c e n t r a t i o n s .
Work i n p r o g r e s s on Phase I w i l l p r o v i d e f u r t h e r
i n f o r m a t i o n on t h e l o n g - t e r m c o r r o s i o n b e h a v i o r o f comm e r c i a l a l l o y s i n CGA e n v i r o n m e n t s . S i g n i f i c a n t l y more
5000 h r d a t a a r e r e q u i r e d a t 0.1 and 1.0 v/o H2S conc e n t r a t i o n s a t 1800F. Data t o 5000 h r a r e a l s o d e s i r a b l e a t 1500 and 1650F, p a r t i c u l a r l y f o r S e r i e s 2 and
3 alloys.
Phase I I - P i l o t P l a n t T e s t i n g .
T h i s phase o f
c o a l g a s i f i c a t i o n m a t e r i a l s e v a l u a t i o n i n v o l v e s expos u r e o f m e t a l s and r e f r a c t o r i e s i n s e l e c t e d t e s t l o c a tions i n current p i l o t plants. Corrosion t e s t i n g i n
t h i s e f f o r t began d u r i n g 1974 w i t h f o u r p i l o t p l a n t s
and now i n v o l v e s s i x : HYGAS, CONOCO COAL, Synthane,
BI-GAS, S t e a m - I r o n ,
Materials evaluatio
phases o f t h e c o a l g a s i f i c a t i o n p r o c e s s .
Test specimens a r e i n s t a l l e d i n t h e c o a l p r e t r e a t m e n t , g a s i f i c a t i o n , gas quench systems, and m e t h a n a t i o n equipment i n
t h e p l a n t s . Three e x p o s u r e s , n o m i n a l l y 1, 3, and 6
months, a t p l a n t o p e r a t i n g c o n d i t i o n s a r e s c h e d u l e d f o r
each t e s t l o c a t i o n . P o s t - e x p o s u r e c o r r o s i o n e v a l u a t i o n
employed i n Phase I I a r e t h e same as t h o s e u s e d i n
o t h e r phases o f t h e I I T R I program, i . e . , m e t a l l o g r a p h y
combined w i t h g r a v i m e t r i c a n a l y s i s .
A summary o f t h e c u r r e n t s t a t u s o f t h e p i l o t p l a n t
t e s t i n g program i s p r e s e n t e d i n T a b l e V. T e s t i n g i n a
t o t a l o f 35 m e t a l and 6 r e f r a c t o r y l o c a t i o n s i n t h e
HYGAS, CONOCO COAL, Synthane, and BI-GAS p l a n t s i s i n
progress.
Second and t h i r d e x p o s u r e s a r e i n p r o g r e s s
i n t h e HYGAS and CONOCO COAL p l a n t s . F i r s t and second
e x p o s u r e s a r e i n p r o g r e s s i n t h e Synthane, BI-GAS,
S t e a m - I r o n , and B a t t e l l e p l a n t s .
P o s t - e x p o s u r e a n a l y s e s have been c o m p l e t e d , o r a r e
i n p r o g r e s s , f o r 55 m e t a l specimen r a c k s p r i m a r i l y from
t h e HYGAS and CONOCO COAL p l a n t s . A n a l y s e s o f s e v e r a l
i n s t a l l a t i o n s from t h e f i r s t e x p o s u r e a t Synthane a r e
i n progress.
C u r r e n t l y , 60% o f t h e r e q u i r e d r a c k s f o r
t h e t h r e e e x p o s u r e s i n a l l p l a n t s have been s h i p p e d t o
t h e p l a n t s and i n s t a l l e d .
C o r r o s i o n d a t a have been g e n e r a t e d f o r m e t a l s i n
the quench systems and r e f r a c t o r i e s i n t h e g a s i f i e r .
However, s p e c i f i c o x i d a t i o n - c o r r o s i o n d a t a i n t h i s
p a p e r w i l l be l i m i t e d t o m e t a l s exposed i n t h e h i g h t e m p e r a t u r e gas phase l o c a t i o n s o f t h e HYGAS and CONOCO
COAL p l a n t s . A g a i n , t h e r e s u l t s r e p o r t e d w i l l emphas i z e t r e n d s i n d i c a t e d by t h e p i l o t p l a n t e x p o s u r e s .


Start-up
42
24
_2
12
53
273
43
10
60
12
_6_
58
racks.
46
12
158
43
55
2
1
111
--8
12
30
--
12
4
1.2
45
25
2
23
11
30
28
16
31
1.3
2,3
Specimen Racks
Installed
Analyzed
Exposure Metals Refr, Metals Refi
31
58
31
Shipped
Âdded t o t e s t program December,. 1976.
Total
Battelle
Steam-Iron*
BI-GAS
Synthane
CONOCO COAL
HYGAS
Plant
Total
Locations
Total
Metals Refr. Required
CURRENT STATUS OF PHASE I I PILOT PLANT TESTING PROGRAM
Table V
406
A t y p i c a l r a c k employed f o r i n s t a l l a t i o n o f spec
imens i n p i l o t p l a n t s i s shown i n F i g . 6. B o t h c o r r o
s i o n coupons, 2 1 0.35 i n . t h i c k , and bend s p e c i
mens i n t e n d e d t o d e t e r m i n e s t r e s s - c o r r o s i o n c r a c k i n g
s u s c e p t i b i l i t y , are included i nthe i n s t a l l a t i o n f o r
aqueous c o r r o s i o n t e s t i n g . Specimens a r e s e p a r a t e d by
high density alumina spacers t o e l i m i n a t e electrochemi
c a l e f f e c t s . During exposure, t h e racks are welded t o
e x i s t i n g components i n t h e p i l o t p l a n t equipment.
H i g h - t e m p e r a t u r e gas phase o x i d a t i o n - c o r r o s i o n
d a t a have been o b t a i n e d f o r two e x p o s u r e s i n t h e CONOCO
COAL p l a n t and one e x p o s u r e i n t h e HYGAS p l a n t .
Table
VI summarizes t h e o p e r a t i n g e n v i r o n m e n t s and i n - p l a n t
t i m e s f o r t h e s e e x p o s u r e s . S i n c e t h e p i l o t p l a n t s op
e r a t e a t v a r i a b l e t e m p e r a t u r e s , p r e s s u r e s , and gas com
p o s i t i o n s , w e i g h t e d average v a l u e s a r e g i v e n f o r t h e
p l a n t exposures.
Linearly extrapolate
t h e 1150 h r f i r s t exposure i n t h e HYGAS g a s i f i e r o f f gas a r e p l o t t e d i n F i g . 7. I n t h i s l o c a t i o n a t 580F
(average) c a r b o n s t e e l , A I S I 410, A I S I 304, IN-800, and
titanium e x h i b i t e d very l i m i t e d corrosion. A l l o y IN600 and Monel 400 h a d c o r r o s i o n r a t e s o f 42 and 124 mpy,
respectively.
T e s t exposure o x i d a t i o n - c o r r o s i o n d a t a f o r s e l e c t e d
a l l o y s i n t h e f l u i d i z e d b e d o f t h e HYGAS g a s i f i e r a r e
shown i n F i g . 8. A l l o y s exposed i n t h i s l o c a t i o n a r e
d i f f e r e n t from t h o s e i n t h e g a s i f i e r o f f - g a s because o f
t h e h i g h e r o p e r a t i n g t e m p e r a t u r e . The f l u i d i z e d b e d
represents t h e highest operating temperature o f t h e four
t e s t l o c a t i o n s i n t h e HYGAS g a s i f i e r .
First-exposure
d a t a , however, i n d i c a t e r e l a t i v e l y m i n o r c o r r o s i o n o f
A I S I 430, A I S I 309, IN-600, A l l o y X, and RA-333 o f 4 t o
18 mpy. A g a i n , IN-600 showed e x t e n s i v e a t t a c k ( c o m p l e t e
c o r r o s i o n o f 0.250 i n . t h i c k specimens) i n 1720 h r o f
p l a n t o p e r a t i o n d u r i n g t h e f i r s t e x p o s u r e . Thus, I N 600 ( N i - 1 6 C r ) e x h i b i t e d s e v e r e c o r r o s i o n o v e r t h e e n t i r e
o p e r a t i n g t e m p e r a t u r e range o f t h e HYGAS g a s i f i e r . A l
though n o t shown i n F i g . 8, IN-601 ( N i - 2 3 C r - l A l ) h a d a
c o r r o s i o n r a t e o f 12 mpy i n t h e HYGAS f l u i d i z e d b e d .
Two e x p o s u r e s have been c o m p l e t e d i n b o t h t h e
CONOCO COAL g a s i f i e r and r e g e n e r a t o r .
L i n e a r l y extrap
o l a t e d c o r r o s i o n r a t e s f o r s e l e c t e d a l l o y s exposed i n
t h e s e CONOCO COAL t e s t l o c a t i o n s a r e p r e s e n t e d i n F i g s .
9 a n d 10. The d u r a t i o n o f e x p o s u r e i n t h e s e t e s t l o c a
t i o n s was about 800 and 1600 h r i n t h e f i r s t and second
exposures, r e s p e c t i v e l y .
F i g u r e 9 shows t h a t t h e c o r r o s i o n r a t e s i n t h e
CONOCO COAL g a s i f i e r were r e l a t i v e l y l o w f o r b o t h expo
sures.
The a p p a r e n t r e d u c t i o n i n c o r r o s i o n r a t e f o r

HILL E T AL.
Figure 6.
Coal-Gasification
Plants
Typical corrosion specimen rack for Phase II pilot plant exposures

407
CORROSION
408
CHEMISTRY
Table V I
CORROSION CONDITIONS IN CONOCO COAL
AND HYGAS PLANT EXPOSURES
Temp. ,
F
Exposure
Location
Press.,
psi
Time,
hr
CONOCO COAL P l a n t
Gasifier,
off-gas
a
Regenerator^
1425
150
1600
1850
150
800
1850
150
1600
HYGAS P l a n t
Gasifier,
fluidized bed
Gasifier,
off-gas^
a
Gas
1340
980
1718
580
980
1150
c o m p o s i t i o n :i
4 8 H , 23H 0, 12CH4, 8.5CO, 6 C 0 ,

2 5 N , t r a c e H S (v/o)
2
^Gas c o m p o s i t i o n !r
c
Not
^Gas
7 0 N , 2 5 C 0 , 5C0, t r a c e H2 S (v/o)
2
analyzed,
composition :
20.4H , 40,6H 0, 9.3C0 , 2 .5C0,

5,2CH., 4,2N , 0. 1H S, 17. 7 o i l s
Cv/o)
2
0
2

12.
Coal-Gasification
HILL ET AL.
C Steel
Figure 7.
410
304
409
Plants
600
800
Monel
400
Linearly extrapolated corrosion rates of selected alloys in HYGAS

gasifier, off-gas
c.c.
430
Figure 8.
Titanium
309
800
RA-333
Alloy X
600
Linearly extrapolated corrosion rates of selected alloys in

gasifier, heat exchanger bed

HYGAS
410
ce
IN-800
Figure 9.
310
310(A1)
304
ce
IN-671
Alloy X
Linearly extrapohted corrosion rates of selected alloys in

COAL regenerator, off-gas
IN-800
Figure 10.
IN-800(A1)
ce
IN-800(A1)
310
310(A1)
304
IN-671
Linearly extrapohted corrosion rates of selected alloys in

COAL gasifier, off-gas
CONOCO
Alloy X
CONOCO

12.
HILL E T A L .
Coal-Gasification
Plants
411
the l o n g e r second e x p o s u r e f o r most a l l o y s was due t o

l i n e a r e x t r a p o l a t i o n o f m e t a l l o g r a p h i c a l l y determined
t o t a l c o r r o s i o n . A p p a r e n t l y , t h e time dependence o f
t o t a l c o r r o s i o n f o r most a l l o y s t e n d e d t o be p a r a b o l i c
r a t h e r than l i n e a r .
For b o t h e x p o s u r e s i n t h e g a s i f i e r , c o r r o s i o n o f
pack d i f f u s i o n a l u m i n i z e d A I S I 310 and IN-800 was
g r e a t e r t h a n t h e u n c o a t e d base a l l o y s .
Metallographica l l y , t h e a l u m i n i z e d c o a t i n g s a p p e a r e d t o be p r e f e r e n t i a l l y attacked; corrosion o f the coated layers termin a t e d a t t h e base m e t a l i n t e r f a c e d u r i n g b o t h e x p o s u r e s .
The c o a t i n g s on IN-800 tended t o be c o m p l e t e l y conv e r t e d t o s c a l e , whereas t h o s e on A I S I 310 were l o c a l l y
penetrated along short c i r c u i t d i f f u s i o n paths.
C o r r o s i o n d a t a f o r t h e CONOCO COAL r e g e n e r a t o r i n
F i g . 10 i n d i c a t e s i g n i f i c a n t l h i g h e c o r r o s i o
durin
the l o n g e r second e x p o s u r e
IN-800, IN-671, A l l o y
,
were c o m p l e t e l y c o r r o d e d d u r i n g t h e second e x p o s u r e .
IN-671 a l s o c o m p l e t e l y c o r r o d e d d u r i n g t h e f i r s t expos u r e . I n c o n t r a s t t o t h e g a s i f i e r , pack a l u m i n i z e d
A I S I 310 and IN-800 d e m o n s t r a t e d t h e b e s t c o r r o s i o n
r e s i s t a n c e i n t h e second exposure i n t h e r e g e n e r a t o r .
Thus, a l u m i n i z i n g p r o v i d e d v a r i a b l e p r o t e c t i o n i n t h e
CONOCO COAL p l a n t .
To d a t e , v e r y l i m i t e d c o r r o s i o n has been o b s e r v e d
f o r dense r e f r a c t o r i e s exposed i n b o t h t h e HYGAS and
CONOCO COAL p l a n t s .
C a s t a b l e s , b r i c k , and ramming m i x
m a t e r i a l s have r e s i s t e d t h e CGA e n v i r o n m e n t s w i t h l i m i t e d a t t a c k . T h i s was e x p e c t e d s i n c e t h e exposure
t e m p e r a t u r e s o f 1500-1800F a r e r e l a t i v e l y l o w f o r
r e f r a c t o r y m a t e r i a l s . Phosphate bonded m a t e r i a l s ,
o r i g i n a l l y t h o u g h t t o be s u s p e c t f o r CGA s e r v i c e , have
shown no s i g n i f i c a n t d e t e r i o r a t i o n .
Some d e t e r i o r a t i o n
of l o w - d e n s i t y i n s u l a t i n g m a t e r i a l s h a s been o b s e r v e d .
These m a t e r i a l s , however, a r e n o t n o r m a l l y exposed t o
the CGA environment i n p i l o t p l a n t g a s i f i e r s .
For this
r e a s o n , t e s t i n g o f i n s u l a t i n g m a t e r i a l s has been t e r m i nated.
Severe c o r r o s i o n o f s i l i c o n n i t r i d e bonded s i l i c o n
c a r b i d e b r i c k d i d o c c u r d u r i n g t h e second exposure i n
the CONOCO COAL g a s i f i e r and d u r i n g f i r s t exposure i n
the Synthane g a s i f i e r .
Dense b r i c k o f t h i s m a t e r i a l
n e a r l y c o m p l e t e l y d i s i n t e g r a t e d i n about 1600 h r a t
1400-1500F. I n c o n t r a s t , t h e m a t e r i a l s u r v i v e d b o t h
exposures a t 1800-1900F i n t h e r e g e n e r a t o r w i t h o u t
d e t e r i o r a t i o n . These r e s u l t s a r e t h o u g h t t o be due t o
a t t a c k by w a t e r v a p o r i n t h e g a s i f i e r .
F u t u r e c o r r o s i o n d a t a o b t a i n e d from t h e Synthane,
BI-GAS, Steam-Iron, and B a t t e l l e p i l o t p l a n t s w i l l add

412
s i g n i f i c a n t l y to the e x i s t i n g p i l o t p l a n t i n f o r m a t i o n .
Environmental conditions i n these plants d i f f e r
signifi c a n t l y f r o m t h o s e o f t h e H Y G A S a n d CONOCO C O A L p l a n t s .
A c c o r d i n g l y , t h e new p i l o t p l a n t i n f o r m a t i o n w i l l
provide o x i d a t i o n - c o r r o s i o n data for a wider range of
gas
compositions
and o p e r a t i n g
temperatures.
Summary
of
Results
S i n c e the e f f o r t d e s c r i b e d h e r e i n i s an ongoing
p r o g r a m , w e l l - d e f i n e d c o n c l u s i o n s a r e , as y e t ,
inappropriate.
Some t r e n d s , h o w e v e r ,
are r e a d i l y evident i n
o x i d a t i o n - c o r r o s i o n obtained to date i n coal
gasificat i o n atmosphere.
It is clear that coal gasification
e n v i r o n m e n t s a r e much m o r e s e v e r e t h a n a i r a t t h e same
temperatures.
F u r t h e r m o r e , a chromium content of
20
weight percent,
an
high-temperature alloys is required for long-term res i s t a n c e t o CGA e n v i r o n m e n t s .
The r o l e of
secondary
a d d i t i o n s , aluminum, t i t a n i u m , s i l i c o n , molybdenum,
tungsten, etc.,
and r e s i d u a l s such as manganese,
has
not been c l e a r l y e s t a b l i s h e d .
O x i d a t i o n - c o r r o s i o n data obtained from the p i l o t
p l a n t s g e n e r a l l y compare w e l l w i t h l a b o r a t o r y d a t a i n
ranking of high-temperature a l l o y s .
Pilot plant res u l t s , however,
i n d i c a t e more severe c o r r o s i o n than
laboratory oxidation-corrosion data.
T h i s s h o u l d be
expected because of c y c l i c operation of p i l o t plants
and a d d i t i o n a l v a r i a b l e s c o m p r i s i n g the p i l o t p l a n t environments.
The c o n t r i b u t i o n of e r o s i o n and e r o s i o n c o r r o s i o n by c o a l a s h , c h a r , and s u l f u r sorbents to
the
c o r r o s i o n p r o c e s s i n the p i l o t p l a n t s has not been
defined.
Laboratory oxidation-corrosion data indicate that
e x t r a p o l a t i o n of short-term o x i d a t i o n - c o r r o s i o n
data
to yearly rates is d i f f i c u l t .
These e x t r a p o l a t i o n s
are
necessary to p r o v i d e a b a s i s f o r comparing o x i d a t i o n c o r r o s i o n d a t a o b t a i n e d f r o m v a r i a b l e CGA e x p o s u r e
times.
E x t r a p o l a t e d data, p a r t i c u l a r l y at h i g h
H2S
c o n c e n t r a t i o n s i n t h e CGA a t m o s p h e r e ,
s h o u l d be
employed
with caution.
Long-term k i n e t i c s of the o x i d a t i o n c o r r o s i o n process can r e s u l t i n t r a n s i t i o n s i n c o r r o s i o n b e h a v i o r to h i g h r a t e s not p r e d i c t a b l e by
short
exposures.
S i m i l a r behavior, breakaway o x i d a t i o n ,
o c c u r s i n a i r p r i m a r i l y a t temperatures above 2000F.
A c k n o w l e dgment s
to
A.
The
0.
author would l i k e to express h i s

Schaefer of the Metal Properties
appreciation
Council,

12. HILL ET AL.
Coal-Gasification Plants
413
W. R. Hulsizer of the International Nickel Company,

and H. E. Frankel, W. T. Bakker, and S. J. Dapkunas of
the Department of Energy for their helpful suggestions.
IITRI personnel who contributed significantly to this
program include . A. H. Howes, S. Bhattacharyya,
C Hales, and Y. Harada.
Literature Cited
1. Hansen, ., and Anderko, ., Constitution of Bi
nary Alloys," 2nd ed., McGraw-Hill Book Co., New York,
1958.
2. Howes, . . ., and Schaefer, A. O., "Selection of
Materials Used in Coal Gasification Plants," American
Gas Association, Sixth Synthetic Pipeline Gas Symposium,
Chicago, I l l i n o i s , October 1975
3. Parikh, . ., Howes
Schaefer, A. O., "Material
cesses," Paper No. 173, NACE, Corrosion/75, April 1975.
4. Samans, C. ., and Hulsizer, W. R., "Current Pro
gress in Materials Selection for Coal Conversion,"
ASME, Mexico City, September 24, 1976.
5. Hulsizer, W. R., "Developing a Data Base," American
Gas Association, Eighth Synthetic Pipeline Gas Sympos
ium, Chicago, I l l i n o i s , October 1976.
6. H i l l , V. L., and Howes, . . ., "Metallic Corro
sion in Coal Gasification Pilot Plants," Paper No. 50,
NACE, Corrosion/77, March 1977.
7. Bhattacharyya, S., Bock, F. C., MacNab, ., and
Cox, T. B., "Alloy Selection for Coal Gasification
Quench Systems," Paper No. 51, NACE, Corrosion/77,
March 1977.
8. H i l l , V. L., "Corrosion and Erosion-Corrosion of
Materials i n Coal Gasification Environments," American
Gas Association, Ninth Synthetic Pipeline Gas Sympos
ium, Chicago, I l l i n o i s , October 1977.
9. Bhattacharyya, S., H i l l , V. L., Humphreys, . .,
and Hamel, F. B., "Aqueous Corrosion in Coal Gasifica
tion Pilot Plants," American Gas Association, Ninth
Synthetic Pipe Gas Symposium, Chicago, I l l i n o i s ,
October 1977.
RECEIVED
September 1, 1978.

INDEX
A
Acetylenic compounds, formation of
polymerous layers with
292f
Acetylenic inhibitors
288, 302/
Acquisition rate, molar
105
Activation
control, anodic partial process
under
65
controlled partial processes
59
energy diagrams
136/
energy for hydration
162
overpotential
135
Active state, characterization of
166
Activity (ies) of
cupric ion
45
ferrous and ferric ions
46/
water
43/
Adsorption
182
of corrosion products formed on
NiFe, IR
242/
isotherms
248/
measurements, indirect
300
mechanism involving an ion
exchange step
318
theory
159,161,300
Air-cooled radiator section
366/
Airfoil-stress-corrosion cracking
2
Airplane turbine engine applications ..
92
Alkyl propylenediamines and water
soluble amines as process corrosion inhibitors, effectiveness of .... 317/
Alloy-oxide interface
91
Alloys
chemical composition of
395f
corrosion rates of
402i, 409/, 410/
oxidation of
88
passivity on
162
weight change of selected
400/
Aluminum
alloy(s)
aqueous corrosion of
219/
corrosion of
207/
high-temperature film breakdown
for
228
high-temperature pitting for
228
parabolic corrosion of
197/
paralinear corrosion of
199/
corroded surface of "commercially
pure"
227/
Aluminum (continued)
corrosion of
early stages
corrosion rate constant for
failures
galvanic corrosion of
intermetallic compounds, cathodic
polarization curves for
long-time corrosion of
low-temperature corrosion of
oxide platelets on
resistance for growing barrier
films on
Amines, lipophilic
197/
201/
214/
377
241/
219/
202/
200
191/
188/
316
diamines and water soluble

317f
Analog circuit
103
Anion/water ratio
168
Anode behavior
169/
Anodic
-cathodic equilibrium
14
-cathodic reactions, battery
15/
dissolution
128/, 138/
inhibition
143,272,274/
partial process
58
under activation control
65
passivation
137
curves
138/
polarization
141/, 345
process
16
protection
153,156
reactions
50
polarization curves
136/
Tafel slopes
305
Aqueous adsorbate
255
Aqueous corrosion of aluminum alloy 219/
Arrhenius
dependence
106
equation
134
plot
215
Atmospheric cooling tower
355i
Atmospheric corrosion
data
235
summary of
239
measured by light scattering
240/
resistant to
239
water in
258
role of
235
Atom polarizability
21
414

415
INDEX
Auger of cobalt
Auger electron spectroscopy
242/
32, 239
Battery
anodic-cathodic reactions
electrode
mixed potential
lead-acid
storage
Behavior, solid material
B E T model
Blisters
Blowdown
Boehmite
Boiler-feed-water stabilizations
Bond energy
metal-oxygen
Brass, dezincification of
Buffer solutions
Bulk diffusion
controlled process
processes
14
15/
18/
19
18/
14
7
255
215
365
200
2
187
190/
37
141
76
82
94
C
Calcium carbonate scale control
357
Cathodic
-anodic equilibrium
14
-anodic reactions, battery
15/
inhibition
272,274/
partial process
53, 55/
under transport control
65
partial reaction
57
polarization
345
curves for aluminum intermetallic compounds
219/
process
16
protection
156
reactions
50
reduction
142,144/
Tafel slopes
305
Cavitation corrosion
376/, 386
attack
388/
damage
375/
prevention of, soluble oil type
389
protection against
389
vibratory
387/
Cell-battery applications, fuel
98
C G A (coal gasification atmosphere) .. 401
Characterization of active and
passive states
166
Characterization of passivating films .. 160/
Charge flowing, total
342/
Charge transfer
21
processes
293
Chelate-metal inhibitor structure
307
Chemical
composition of alloys
potential of oxygen
process of scaling, electrical
formulation of
Chemisorption
Chemistry of corrosion inhibitors
Circuit
analog, dc
conditions, open
equivalent
approach
description
models, kinds of
potentiostatic
theory, closed
theory, open
of parabolic oxidation
Clean system concept
395i
87/
101
162
315
43/
Ill
117
118
101
100
Ill
155/
116
96
107
361
circuit theory
116
cooling systems
351
recirculating
362
system radiator section
367/
Coal gasification
atmosphere ( C G A )
401
materials research
392
plants
92,391
Coals, high-sulfur
392
Coatings
348
Cobalt, Auger of
242/
Coefficients, diffusion
84
Colloid, hydrated
228
Complexing agent, versene, effect
on passivation
145/
Compound-electrolyte interface
26/
Compounds, rate constants for forma
tion of metal-nonmetal
109i
Concentration cell(s)
368,373/
corrosion damage
374/
metal ion
372/
oxygen
372/
Conduction, mixed
medium
112
transport in
112
processes
105
in solids
100
Conductivity (ies)
dependence of total
108/
electronic
83/
-emf-transference number data
98
independent ionic
107
partial
dependence of
198/
partial pressure dependence of .... 105
temperature dependences of
105
product, transference number-total 116

416
Conductors under closed circuit conditions, multicomponent mixed .. 110

Conductors, mixed ( ionic and
electronic)
100
Constant current (see Galvanostatic)
Cooling
water, high-temperature364
water treatment programs,
objectives
351
system(s)
closed-recirculating
362
corrosion inhibition
360
double recirculating
356/
heat exchanger, clogged
363/
open-recirculating
352
tower(s)
atmospheric
355/
closed cooling systems
352
induced draft
353/
natural draft
354
open-recirculating
35
Copper-cupric ion reaction
44
Correlation between inhibitor constitution and inhibitor activity
293
Corroded surface of "commercially
pure" aluminum
227/
Corroding surfaces
2
Corrosion
1,129,381/
acceleration of
285
strong complexing agents, E D T A
salts
285
of aluminum
197/, 201/
alloy
aqueous
219/
parabolic
197/
paralinear
199/
low temperature
200
cavitation
376/, 389
attack
388/
damage
375/
prevention of, soluble oil type .... 389
protection against
389
vibratory
387/
chemical criterion of
35, 37
concentration cell
371
damage
374/
conditions, plant exposures
408i
control
360
cooling system water treatment .. 358
crevice
385/
of Croloy
194/
current
19
density
60, 67
definition of
35,47,126, 264
effect(s) of
applied current on
232/
hydrogen sulfide concentration on 399/
temperature on
398/
Corrosion (continued)
electrochemistry of
209
engineer
3,4/, 6/, 7,31
fatigue
339,348
-fracture processes
36
high-temperature
76, 391
"immune" to
47
inhibiting paints
2
inhibition
126,143,144/, 262
cooling system
360
definition of
263
formation of oxide
films
126
phenomena
263
in presence of hydrogen sulfide .. 307
inhibitors
chemistry of
315
classification of
266
effectiveness of alkyl propylenediamines and water soluble
polyphosphates
359
of iron
126, 306/
isothermal
94
kinetics
35
lecture classifications
13/
localized
147
mechanism
263
mitigation
47
mixed potential process
63/
oxide removal, influence of
199/
paralinear
200
and potential, relationship between 146/
potentials
2,14,66
process (es)
214/
electrochemical kinetics of
58
kinetics of
263
metallic
58
products formed on NiFe, IR
adsorption of
242/
rate(s)
60,66,129,139,198
of alloys
402*, 409/, 410/
constant for aluminum
214/
vs. inhibitor concentration
279
of iron
160/
of parabolic
92
of steel
286/
of uranium
220/
reactions, anodic oxidation
264
reactions, cathodic depolarization .. 264
resistance
193,196,215
response
236
specimen rack
407/
studies, electrochemical techniques
in
35
system(s)
15/
multiple partial process
67
terminology
3,5/

INDEX
417
Corrosion (continued)
testing, laboratory hightemperature
tests
of valve metals
"worm hole"
Corrosive gas
Coulometry
Crack
path of, intergranular
path of, transgranular
propagation
velocity
Cracking
airfoil-stress-corrosion
mechanism of
stress-corrosion
393
231/,394i
185
386
76
175/
323
323
334
328, 345
127, 381/, 382/
2
340
36,127,149,
321,327/, 406
in aqueous media
321
mechanisms
33
systems for
32
systems exhibiting
325i
Creep strain-rate
349
Crevice corrosion
385/
Croloy, corrosion of
194/
Croloy-5
193
Crystal lattice
97/
Crystalline salt phase
27
Current
48
density
52
corrosion
67
instantaneous
flux
71
-potential curves
181/
lines, potential-log
16
-potential curves
180
potential diagram
280/
Curves, anodic passivation
138/
D
Data
on atmospheric corrosion
235
galvanostatic
72/
potentiostatic
72/
Decohesion
343
Defect chemistry
90
Degradation, rate of oxide-film
178
Density, corrosion current
60
Dependence of partial conductivities 108/
Dependence of total conductivities .... 108/
Deposition
360
Dezincification
378/
of brass
371
layer type
377
plug type
377, 379/
Diagram ( s )
activation energy
136/
Evans
135, 269-271
Diagram(s) (continued)
polarization
63/, 68/
Pourbaix (see Pourbaix diagrams)
ternary
121/
Diesel engines
364
Diffraction, electron
141/
Diffusion
coefficients
84
controlled
91
kinetics
76
process, bulk
82
data, radiotracer
86
processes, bulk
94
tracer
83/
Diffusivity
116
Dipole orientation
21
Direct current (dc) analog
119/
Disorder
anti-Frenkel
81
Frenkel
79
Schottky
79
Displacement reaction
92,93/
Dissociation pressure of oxide
87/
Dissociation reactions, local
equilibrium of
114
Dissolution
203
anodic
128/, 138/
definition of
126
direct
130
of iron
126
kinetics
134
metal
136/
of metal lattice
162
of oxides, reductive
142
rate
179
reaction, predict
129
by separate steps
130
Tafel slope of free
177
Double recirculating cooling system .. 356/
Dry oxidation
235
E d d y current
Electric field, at interface
Electrical formulation of chemical
process of scaling
Electrochemical
behavior, effect of oxidizer
concentration on
behavior, effect of velocity on
cell
thermodynamic voltage of
condition, definition of
kinetics
of corrosion processes

200
39
101
157/
'. 158/
119/
121/
113
48
58
418
Electrochemical ( continued )
oxidation
47, 50
polarization systems
69, 70/
reactions
14,16, 41
techniques in corrosion studies
35
thermodynamics
38
Electrochemically active chemical
species
42
Electrochemistry of corrosion
209
Electrochemistry, solid-state
99
Electrode
conditions, ion blocking
117
exchange kinetics
Ill
polarizable
21,22/
potential ( s ) ( see also Potentiostatic)
14,38,39,43/
at 2 5 C
40f
-current relationships
14
equilibrium
40, 44
measurements
6
reactions
49/
control of
57
properties of
48
reference
69, 271
standard hydrogen ( S H E )
39
surface
11,21
test
43/, 69,154
working
271
Electrodedeposition of iron
142
Electrolysis ( charging mode )
115
Electrolyte
applications, high-temperature
solid
110
emf sensors, solid
110
fuel cells, solid
105
resistance, effect of
273/
two-anion
122
Electrolytic cell, multicomponent
mixed conducting
119/
Electrolytic plating
27, 28/
Electron
density
23
diffraction
141/
low energy ( L E E D )
32
microscope, scanning
32
spectroscopy for chemical
analysis ( E S C A )
32
Electroneutrality, laws of
265
Electronic(s)
conduction
96
conductivity
83/
semiconductor
23
transference numbers
98
Electropolishing
127,137
Electrosorption, van der Waals
267
Ellipsometer
172/
Ellipsometric parameters
171
Ellipsometry
164,236
Embrittlement
127
hydrogen
340,343
metal
156
emf sensors, solid electrolyte
110
emfs, thermocouple
114
Engines, internal compustion
365
Equilibrium
approach, local
112
electrode potential
44
of dissociation reactions, local
114
reaction, metal-metal ion
44
Equivalent circuit
118
approach
101
description
100
Erosion-corrosion
391
E S C A ( electron spectroscopy for
chemical analysis )
32
Evans diagram
135,269-271
Evans polarization curves
132/
Evaporative systems
362
Exfoliation
381/, 382/
F
Failure, stress-corrosion
Faradaic processes
Faraday
constants
Ferric ion reduction
Ferrous passivation
Film(s)
on aluminum, resistance for
growing barrier
breakdown
for aluminum alloys, hightemperature
localized
characterization of passivating
degradation of
formation of oxide
-forming metals
-forming reaction
fracture, corrosion
growth
and degradation of oxide
Tafel slope for
with pore, reaction on
reduction
repair
thicknesses
unstable in aqueous solution
Filming amines
Fitting
Flade potential, definition of
Flade relation
Formation of metal-nonmetal compounds, rate constants for

338
21
113,159
40, 269
67
153
188/
139,140
228
149
160/
196
196
185
177
340, 344
171
189
190/
151/
171
140
187
187
308
383/
154
169/
109f
419
INDEX
Formation, solid phase
27, 28/, 30/
Fracture toughness
326
Free
-energy conditions, zero
114
-energy data, thermodynamic
14
enthalpy
35
standard
36
Frenkel
defect
97/
Disorder
79
anti81
notion
96
Fretting attack
380, 384/, 385/
Freundlich isotherm
295
Fuel cell-battery applications
98
Fuels cells, solid electrolyte
105
G
Galvanostatic ( constant curren
data
72
Gas
corrosive
76
permeability studies
109
phase
11
Gasification environments, behavior
of high-temperature materials in 392
Gibbs-Duhem relation
101
Gold, water adsorption on
252/
Guy-Chapman double layer theory .... 262
H
Heat exchanger, cooling systems,
clogged
363/
Helmholz double layer theory
262
High coolant velocity
369/
High-temperature
-cooling water
364
corrosion
391
testing, laboratory
393
materials in gasification environments, behavior of
392
solid electrolyte applications
110
Hydrated oxides
187
Hydration, activation energy for
162
Hydrogen sulfide
concentration on corrosion, effect of 399/
corrosion inhibition in presence of 307
corrosion of iron in presence of
309
Hydrolysis systems
105
I
Ideal solution
"Immune" to corrosion
Immunity
256
47
129
Imperfections on solid surfaces

128/
Impingement attack
373/
definition of
368
Impurities, surface
127
Independent ionic conductivity
107
Indium, anodic dissolution of
283
Induced draft cooling tower
353/
Industrial problems
351
cooling water
351
stress-corrosion cracking
321
Influence of corrosion oxide removal.. 199/
Inhibiting paints, corrosion
2
Inhibition
274/
anodic
272
cathodic
272
of corrosion
126,143,144/
formation of oxide
films
126
decreasing
289i
electrolyte-layer
268
causes of
267t
of iron corrosion
296/
mechanism, importance of hydroxyl
group
291
by thiourea and quinoline
derivatives
277
Inhibitor(s)
276/, 278/
acetylenic
288
activity and inhibitor constitution,
correlation between
293
amine
271
anodic
143
concentration vs. corrosion rate
279
concentrations, man-failures in
maintenance of
371
constitution and inhibitor activity,
correlation between
293
dangerous
347
definition of
126
interaction with iron sulfide surface 314
nonoxidizing
147,148/
oxidizing
147,148/
propargyl alcohol
306/
safe
347
Interface
alloy-oxide
91
compound-electrolyte
26/
metalcompound
24
metal oxide
80/
oxide
77
solution
39,48
oxide-gas
77, 80/
solid-electrolyte
23
Ion
blocking electrode conditions
exchange resin

117
198
420
Ion (continued)
exchange step, adsorption
mechanism involving
318
movements
21
Ionic
absorption
21
compound scale
99
conduction
96
conductivity, independent
107
migrations
101
transference numbers
98
Iron
-chromium alloys
193,195/
corrosion
126, 302/, 306/
in H S
311/
inhibition of
282, 296/
rate of
160/
dissolution of
126
electrodeposition of
142
-ferrous ion reaction
4
passivation
13
Pourbaix diagram
44,47,49/, 132/, 212
in presence of hydrogen sulfide,
corrosion of
309
sulfide surface, inhibitor interaction
with
314
Isothermal corrosion
94
Isotherms, adsorption
248/
water
245
i - V curve
155/, 170,180
0
Kinetics
diffusion controlled
electrochemical
of corrosion processes
electrode exchange
of metal oxidation
oxidation
parabolic oxidation
parabolic tarnishing
76
48
58
Ill
254
88
78/
96
L
Langelier Saturation Index
Langmuir adsorption constant
Langmuir models
Lattice, crystal
Le Chatelier's Principle
Lead-acid battery
Lead-acid storage battery
Lead oxide
Linear polarization measurements
Liquid boundary layer, mass flux
across
Liquid phase
Liquid-solid systems
361
294
255
97/
209
18/
14
16
277
313
11
19
Localized corrosion
Localized film breakdown
Low energy electron diffraction
(LEED)
Luggin capillary
147
149
32
69, 70/
M
Man-failures in maintenance of
inhibitor concentrations
371
Marker movement
77
Mass
flux across liquid boundary layer ... 313
transfer coefficient
56, 67
transport control
57
transport-controlled data
66
Materials research, coal gasification .. 392
Materials science
1
Mechanims, definition of
126
cracking
Melt, solidification of
Metal
-compound interface
dissolution
reaction
-electrolyte system
embrittlement
film-forming
hydride, formation of
inhibitor-chelate structure
ion concentration cell
lattice, dissolution of
-metal ion equilibrium reaction
-metal oxide interface
-metal sulfide systems
-nonmetal compounds, rate con
stants for formation of
oxidation, kinetics of
-oxide interface
-oxygen bond energy
passivation of
scaling systems
-solution interface
-solution potential difference
surface of
Metallic corrosion processes
Metallic systems
Microbicides
Microelectrode, glass, silver/silver
iodide, p H
Migration fluxes, steady state
Migrations, ionic
Mitigation, corrosion
Mixed conduction
medium
transport in
processes

338
28/
24
136/
177
11
156
185
212
307
372/
162
44
80/
394i
109i
254
77
190/
71
98
39
166
127
58
42
362
229/
116
101
47
112
112
105
421
INDEX
Mixed conduction (continued)
solids
theory of
Mixed (ionic and electronic)
conductors
Mixed potentials)
battery electrode
systems
Mobility, absolute
Mobility, electric
Models, kinds of circuit
Molar acquisition rate
Monolayer-oxide theories
Morphology of scaling layers
Multicomponent mixed conducting
electrolytic cells
Multicomponent mixed conductors
under closed circuit conditions,
motivating factors
100
110
100
14
19
65
116
116
Ill
105
165
107
119/
110
Natural draft cooling tower

Nernst Equation
Nickel, passivation of
NiFe, IR adsorption of corrosion
products formed on
Nomenclature
Nonelectrochemical methods
Nonmetallic phases
Nonoxidizing inhibitors
Nuclear reactor systems
354/
209
164, 249
242/
73, 74
170
96
147,148/
198
p
Ohms law
Open circuit conditions
Open circuit theory
of parabolic oxidation
Open-recirculating towers
Optical
ellipsometry
photopotential measurement
Overaging, effect of
Oxidation
of alloys
-corrosion data
test exposure
corrosion rates, yearly
cubic
electrochemical
iron foil
kinetics
metal-oxide interface
open circuit theory of parabolic
potential
potentiostatic
rate
120
117
96
107
351
168
168
331/
88
393
406
401
203
47, 50
192/
88
222
107
173/
172/
87/
Oxidation (continued)
steady state
173/
thin-film
187
transient
173/
Oxide(s)
-film
degradation, rate of
178
structure of
140
theory
163
of passivity
159
-gas interface
77, 80/
hydrated
187
platelets on aluminum
191/
protective
94
Oxidizer concentration on electro
chemical behavior, effect of
157/
Oxidizing inhibitors
147,148/
Oxygen
chemical potential of
87/
reduction
Oxyhydroxide surface
11
259
Parabolic
growth law
198
oxidation, open circuit theory of
107
rate constant
89/, 208
scaling, physical processes
99
scaling rate constants
98
tarnishing kinetics
96
Parabolicyit of sulfide corrosion,
minute quantities of oxygen
310
Parameters, water adsorption
250i
Partial
conductivities, dependence of
108/
pressure dependences
106
constant
106
exponential
106
of partial conductivities
105
process ( es)
activation controlled
59
anodic
58
cathodic
53, 55/, 57
corrosion systems, multiple
67
Passivating film, characterization of .... 160/
Passivation
129
anodic
137
"cause" of
156
curves
138/
effect of complexing agent,
versene, on
145/
enforced
154
ferrous
153
iron
137
of nickel
164

422
Passivation ( continued )
phenomena
153
surface
19
theories
159
of titanium, spontaneous
158/
Passive
films
14
state, characterization of
166
state, definition of
156
Passivity
342/
on alloys
162
definition of
47,126
oxide-film theory of
159
Permalloy, water adsorption in
monolayers on
251/
Permeability studies, gas
109
Petroleum industry, corrosion
inhibitors in
308
p H on stress corrosion crack velocity,
influence of
332/
Phase
crystalline salt
2
equilibria
14
gas
11
liquid
11
nonmetallic
96
Physical arrangement, scaling
102/
Pilot plant testing
404
program
405i
Pitting
149,150/, 225,
243, 334, 342/, 371
for aluminum alloys, high
temperature
228
corrosion
339
Plants, coal gasification
92
Plating, electrolytic
27, 28/
Plating, vapor
28/
technique
27
Polarizable electrode
21,22/
Polarization
anodic
141/, 345
cathodic
345
curves
for anodic reactions
136/
Evans
132/
"superposition" of
58
diagram
63/, 68/
intermittent resistance
137
systems, electrochemical
69, 70/
Pollutants cause corrosion
236
Pollution controls
359
Polymerous layers with acetylenic
compounds, formation of
292f
Polyphosphates as corrosion inhibitors 359
Pore, reaction on film with
151/
Potential(s)
-current density curves
181/
difference, metal-solution
166
Potential ( s ) ( continued )
electrode
38, 39, 43/
measurements
69
equilibrium electrode
40
- l o g current lines
16
of oxygen, chemical
87/
systems, mixed
65
Potentiostatic (electrode potential) ..
71
circuit
155/
data
72/
oxidation
172/
Pourbaix diagrams
41, 42, 43/, 44,
45/, 46/, 130,213/
corrosion behavior
130
iron
44, 47,49/, 132/, 212
for F e - ,
167/
regions; corrosion, immunity, and
passivity
47
Powder surfaces
245
Predictive criteria for inhibitor effec
Pressure, oxygen partial
Preventative measures, stress-corro
sion cracking
Problem solving
Protective oxides
Pulse technique
87/
346
3
94
170
Quinoline derivatives, inhibition by ..
277
R
Radiator section, air-cooled
366/
Radiator section, closed-system
367/
Radiotracer diffusion data
86
Raoult's law
256
Rate
constants for the formation of
metal-nonmetal compounds .... 109f
constants, parabolic scaling
98
determining
94
step
93/
film thicknesses
177
limiting
91
oxidation
87/
of oxide-film degradation
178
of parabolic corrosion
92
Reaction mechanisms
131
Redox
50
definition of
38
systems
14
Reduction
cathodic
142,144/
ferric ion
67
oxygen
11

INDEX
423
Reference electrodes
69 Stable species
42
Refractive index
170 Stainless steels
196
Relative humidities, critical
243, 244t Standard
Remote sensor applications
98
electrode potential
41
Repassivation
334, 335/
free enthalpy
36
time
336
hydrogen electrode ( S H E )
39,44
Resistance for growing barrier films
Steady state migration
fluxes
116
on aluminum
188/
Steady state oxidation
173/
Resistant to atmospheric corrosion .... 239 Steel, corrosion rate of
286/
Steel, rest potential of
284/
Stirring
151/
S
Stoichiometry, state of
79
14
Saturation Index, Langelier
361 Storage battery, lead-acid
348
Scale control, calcium carbonate
357 Strain-rate
creep
349
Scale, ionic compound
99
surface
338
Scaling
360
Stress
electrical formulation of chemical
-corrosion
process of
101
cracking
36,127,149,
layers, morphology of
107
physical arrangement
102
rate
99,10
in aqueous media
321
simulated
102/
electrochemistry
322, 323
systems, metal
98
fracture mechanics
322, 323
Scanning electron microscope
32
mechanisms
338
Scattering, atmospheric corrosion
physical metallurgy
322
measured by light
240/
propagation of
335/
Schottky Disorder
79
anti79
systems of
324
Self-diffusion data
86
systems exhibiting
325i
Semiconductor electronics
23
velocity, effect of solution conSemiconductor solid
23
centration upon
333/
Sensor applications, remote
98
velocity, influence of p H on .... 332/
Shock, thermal
94
failure
338
Solid
mechanisms
340
adsorbent
254
susceptibility, testing for
324
electrolyte fuel cells
105
intensity
327/
-electrolyte interface
23
factor
326
material behavior
7
level
346
mixed conduction in
100
sorption
340,344
phase formation
27, 28/, 30/
Structural disorder, anti81
semiconductor
23 Sulfide corrosion, parabolocity of
310
state chemistry
16, 19
minute quantities of oxygen
310
-state electrochemistry
99 Sulfur concentration, high
391
surfaces, imperfections
128/
Sulfuric acid
16
Solidification
29 Surface
of melt
28/
chemistry
16
Solution
electrode
11, 21
composition
129
impurities
127
kinetics
293
concentration upon stress-corrosion
passivation
19
crack velocity, effect of
333/
phenomena
7
precipitation
28/
phenomenological studies
262
viscosity, effect of
330/
states
23
Sound metal loss
397
strain-rate
338
Spectroscopy, Auger electron
32
73,74
Spectroscopy, x-ray photoelectron
32 Symbols
Stability Index
358 Systems exhibiting stress-corrosion
Stabilizations, boiler-feed-water
2
cracking
325f

424
Tafel
behavior
66
constant or slope, cathodic
52
constants (slopes)
51
law
154
line
53
region(s)
61,135,270,271
data
62
slope(s)
14, 65, 189, 270, 277, 279-282
anodic
305
cathodic
305
for film growth
190/
of free dissolution
177
Tarnishing
259
Temkin discharge
176
Temperature on corrosion, effect of .... 398/
Temperature dependences
106
constant
106
exponential
10
of partial conductivities
10
Terminology, corrosion
3,5/
Ternary diagram
121/
Test atmosphere
236
Test electrodes
43/, 69,154, 270
Theory of mixed conduction
110
Theory of passivity, oxide-filmadsorption
165
Thermal shock
94
Thermocouple emf s
114
Thermodynamic ( s )
of active-passive transition
166
electrochemical
38
free energy data
14
voltage
115
of electrochemical cell
121/
Thin-film oxidation
187
Thiourea derivatives, inhibition by .... 277
Time-to-failure
326
Tin pest
365
Titanium, spontaneous passivation of 158/
Total conductivities, dependence of .. 108/
Toxicity
359
Tracer diffusion
83/
Transference number(s)
98,104
-total conductivity product
116
Transient oxidation
173/
Transition, thermodynamics of
active-passive
166
Transport
control, cathodic partial process
under
65
in mixed conduction medium
112
electron migration
112
ion migration
112
numbers
84
processes
87/
Turbine engine applications, airplane

Two-anion electrolytes
92
122
U
Uniform corrosion, definition of
Uranium
alloys, corrosion of
corrosion
rate
59
215
223/
221/
220/
V
Valve metals, corrosion of
185
van der Waals electrosorption
267
van der Waals force
267
Vapor plating
28/
technique
27
Velocity on electrochemical behavior,
effect of
158/
Versene on passivation, effect of
complexing agent
Voltage
of electrochemical cell, thermo
dynamic
-measuring device
thermodynamic
145/
121/
39
115
W
Water
adsorption
on gold
isotherms
in monolayers on Permalloy
parameters
summary of
in atmospheric corrosion
role of
Weight change of selected alloys
"Worm hole corrosion"
"Worm holing" attack
42
235,243
252/
245
251/
250i
257
258
235
400/
386
385/
X
X-ray photoelectron spectroscopy
32
2
Zero-free energy conditions
114
Zinc amalgan, dissolution of
264
Zircaloy-2, corrosion of
206/, 207/
Zirconium
crystal, oxidation of
211/
kinetic behavior
203
oxidation of
208,210/, 224/
poly crystalline
210/
oxide, recrystallization
203


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Corrosion Chemistry

Illinois Institute of Technology

Based on a 1976 lecture series

ACS SYMPOSIUM SERIES

In Corrosion Chemistry; Brubaker, G., et al.;

Library of Congress CIP Data

In Corrosion Chemistry; Brubaker, G., et al.;

ACS Symposium Series

James D. Idol, Jr.

In Corrosion Chemistry; Brubaker, G., et al.;

a m e d i u m for p u b l i s h i n g symposia q u i c k l y i n book form.

papers are n o t typeset b u t are r e p r o d u c e d as t h e y are s u b m i t t e d b y t h e authors i n c a m e r a - r e a d y f o r m .

means of s a v i n g t i m e , t h e papers are n o t e d i t e d o r r e v i e w e d

In Corrosion Chemistry; Brubaker, G., et al.;

w i l l i n t r o d u c e those u n f a m i l i a r w i t h these areas to n e w concepts.

In Corrosion Chemistry; Brubaker, G., et al.;

Corrosion: The Most General Problem of Materials

In Corrosion Chemistry; Brubaker, G., et al.;

and c o n s e r v a t i o n and r e c y c l i n g a r e watchwords, n o t

In Corrosion Chemistry; Brubaker, G., et al.;

In Corrosion Chemistry; Brubaker, G., et al.;

In Corrosion Chemistry; Brubaker, G., et al.;

SURFACE AND SOLID STATE MATERIALS SCIENCE

INORGANIC AND ORGANIC CHEMISTRY

In Corrosion Chemistry; Brubaker, G., et al.;

Corrosion term smorgasbord

THE CORROSION ENGINEER'S RESPONSIBILITY

Corrosion engineers responsibility

In Corrosion Chemistry; Brubaker, G., et al.;

In Corrosion Chemistry; Brubaker, G., et al.;

In Corrosion Chemistry; Brubaker, G., et al.;

Corrosion smorgasbord (continued)

Compact Double Layer

In Corrosion Chemistry; Brubaker, G., et al.;

Corrosion smorgasbord (continued)

Phenomenological view of a one-dimensional solid contrasts with the

In Corrosion Chemistry; Brubaker, G., et al.;

In Corrosion Chemistry; Brubaker, G., et al.;

In Corrosion Chemistry; Brubaker, G., et al.;

Corrosion lecture classifications

In Corrosion Chemistry; Brubaker, G., et al.;

The p e r s p e c t i v e o f s i m p l e phases and phase e q u i l

LEAD-ACID STORAGE BATTERY.

T h i s system p e r m i t s b r i e f d e s c r i p t i o n s o f some key

At the n e g a t i v e lead i s o x i d i z e d t o lead s u l f a t e d u r i n g

In Corrosion Chemistry; Brubaker, G., et al.;

LOCAL REGION SOLID SURFACE TRANSFORMATIONS

Solid 1-Solid 2-L

S o l i d 1-Solid 2-L-G S o l i d 1-Solid 2-G

Model battery anodic-cathodic

In Corrosion Chemistry; Brubaker, G., et al.;

In Corrosion Chemistry; Brubaker, G., et al.;

Short circuit of battery terminals creates characteristic short circuit

In Corrosion Chemistry; Brubaker, G., et al.;

Simple cell in a lead-acid battery

Hydrogen and oxygen evolution reactions at the battery electrode

In Corrosion Chemistry; Brubaker, G., et al.;

In Corrosion Chemistry; Brubaker, G., et al.;

:*Outer Helmholtz Plane

Modeh for the electrical double hyer at a metal surface

In Corrosion Chemistry; Brubaker, G., et al.;

In Corrosion Chemistry; Brubaker, G., et al.;

Electrical double layer with structure introduced on the metal side